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You are on page 1of 104

PH 502

Wavemechanics & Quantum Physics

COURSE SCRIPT

Syllabus

7. The Foundations and Postulates of Quantum Mechanics:

7.1

7.2

Operators and Eigenfunctions:

7.2.1

Properties of Operators

7.2.2

Eigenfunctions and Eigenvalues

7.2.3

Linear Combinations

7.2.4

Orthogonality, Normalisation and Orthonormality

7.2.5

Hermiticity

7.2.6

Commutators

7.2.7

List of Important Operators

7.3

7.3.1

7.3.2

7.3.3

7.3.4

8.

Wavefunction

Physical Systems

Schrdingers Equation

Probability and Expectation Value

7.4

7.4

Dirac Notation

Confined Particles

8.1

E.1

9.

8.2

8.2.1 Example Quantum Corrals

8.3

9.1

9.2

Classical Description

1D Harmonic Oscillator in QM

9.2.1

Solution of Hermites Differential Equation

9.2.2

Correspondence Principle

9.3

9.4

10.1

10.2

E2: Excursus: Co-ordinate Transforms of the Laplacian Operator

E2.1

Method 1: Explicit Solution for 2D Circular Co-ordinates

E2.2

Method 2: Curvilinear Co-ordinate Transforms

10.3

10.4

10.5

Angular Momentum

11.1

11.2

11.3

11.4

11.5

11.5.1 The Periodic Table of Elements

11.6

Electron Spin

11.5.2 Selection Rules and Atomic Spectra

page: 1

Useful constants

Planck constant:

6.62607610-34 Js = 4.13566910-15 eV s

h

h=

h

2

1.05457310-34 Js = 6.58212210-16 eV s

2.99792458108 m/s

Electron mass:

me

9.10939010-31 kg

510.9991 keV/ c2

Proton mass:

mp

1.67262310-27 kg

938.2723 MeV/ c2

Neutron mass:

mn

1.67492910-27 kg

939.5656 MeV/ c2

Fundamental charge:

1.60217710-19 C

Compton wavelength:

C =

Boltzmann constant:

kB

1.38065810-23 J/K

Vacuum permittivity

8 .854188 10 12 C2 /(Jm )

4 0

1 .112650 10 10 C2 /(Jm )

h

me c

2.4263105810-12 m

combinations:

hc = 1.986410-25 Jm = 1239.8 eV nm

h c = 3.161510-26 Jm = 197.33 eV nm

page: 2

Greek Alphabet/Units

page: 3

A

alpha

nu

beta

xi

delta

omicron

gamma

pi

epsilon

rho

zeta

s, V

eta

tau

q, J

theta

upsilon

iota

kappa

chi

lambda

psi

mu

omega

sigma

f, phi

Units

Prefix

Exponent Symbol

deci

centi

milli

micro

nano

pico

femto

atto

zepto

yocto

-1

-2

-3

-6

-9

-12

-15

-18

-21

-24

d

c

m

n

p

f

a

z

y

Prefix

Exponent Symbol

deca

hecto

kilo

mega

giga

tera

peta

exa

zetta

yotta

1 = 10-10 m

1

2

3

6

9

12

15

18

21

24

da

h

k

M

G

T

P

E

Z

Y

page: 4

COURSE SPINE

What is that?

This section is designed to give you a coarse outline of the learning outcomes of each section. You

might find this useful for exam preparations and revision.

From the PDF-File you can always link to

Blue colour provides links to the particular section!

The following symbols mean:

Workshop or exercise

Classical wave mechanics (PH 301)

7.

of Quantum Mechanics:

Definitions and examples

To know:

1. Properties of operators, notation

2. Eigenfunctions and eigenvalues, degeneracy, physical meaning

3. Linear combination

4. Orthogonality, normalisation and orthonormality

5. Hermiticity, real eigenvalues

6. Commutators

7. Important operators: x , y , z , p x ,p y , p z , L x , L y , L z , H , K , U

7.3/7.4

Definitions and examples

To know:

1. Wavefunction, probability interpretation, normalisation

2. Hermitian operators and physical observables

3. Expectation values and deductions

4. Schdinger equations

5. Uncertainty principle (as in (7.4.1))

page: 5

7.2 Operators

page: 6

What is an operator?

An operator is a symbol that tells you to do something to whatever follows the symbol.

More mathematically it can be understood as a symbol that represents a rule to transform a following

function into another function.

and an expression like A

f will be referred to as A

The notation in this script for operators is A

representing a vectoroperating on f . For rigorousity we will very often use symbols like A

operator. The underline shall simply remind you that this operator may act differently on individual

co-ordinates (or vector components).

Scalars and Functions:

A linear function converts a scalar into another:

b = f(a)

A matrix is a linear vector function, thus it converts a vector into another:

b=Ma

b1

m11

b

m

3

31

m12

m22

m32

m33 a3 m31 a1 + m32 a2 + m33 a3

An operator is a function of higher order, thus it generally converts a function into another function:

a( x )

b( x) = M

In quantum mechanics, physical observables (e. g. energy, position, linear and angular momentum)

are represented mathematically by operators. For example the total energy (kinetic energy K plus

, where H is called Hamiltonpotential energy U) is represented by an operator H = K + U

operator or simply Hamiltonian. It is defined as:

7.2 Operators

page: 7

h2 2

H=

+U

2m

We will later derive this formula. The link to experimentally assessable values of the energy (its

average value) of a system described by H and in a state described by a wavefunction (r) is given

.

by its expectation value H

= * (r) H

(r ) dr

H

Most of the properties of operators are obvious. Nevertheless, they are summarised for

completeness:

and B :

Sum and Difference: of two operators A

(A + B ) f = A f

(A B ) f = A f

f

+ B

f

B

[ ]

B

f =A

B

f

A

(7.2.1)

(7.2.2)

on the result of B

f.

which means: First operate with B

f =B

f

Equality: Two operators are equal if A

(7.2.3)

(7.2.4)

, e.g.

The nth power of an operator A

[ ]

2f = A

A

f =A

A

f

A

(7.2.5)

The exponential of an operator exp( A

2

3

) = e A = I + A

+ A + A +K

exp( A

2!

3!

The associative law holds for operators:

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

(7.2.6)

7.2 Operators

page: 8

( ) ( )

B

C

f = A

B

C f

A

(7.2.7)

B

f B A

f

A

(7.2.8)

see commutators!

Examples:

f ( x) = f ( x) + c

1) Addition of a constant: A

d

2) Derivative (wrt x): D f ( x) =

f ( x ) = f ( x ) (could be named prime operator or dot

dx

operator for derivatives wrt time)

3) For D operating on f(x) =exp(ax):

d

D f(x) = D exp (ax ) =

exp (ax ) = a exp (ax ) = a f(x)

dx

4) For D 2 operating on f(x) =exp(ax 2):

exp ax 2 = D

d exp ax 2 = D

2 a x exp ax 2

D 2 f(x) = D D

dx

d

= 2a

x exp ax 2 = 2a exp ax 2 + ax 2 exp ax 2 = 2a 1 + ax 2 f(x)

dx

d2

D 2 corresponds to the second derivative D 2 =

dx 2

[ ( )]

( ) [

( ( )) ( ( )

( )]

( ) (

HINT: To calculate pure operator expressions it is good advice to include a virtual function

(e.g. f) to remind you that you have to operate!

d

Example: For the two operators D

and x x (meaning just multiply with x) calculate

dx

:

D x - x D

[x f ] = D

[xf ] = f + xf

D

f = x [ f ] = xf

x D

x - x D

f = f and D

x - x D = 1

hence : D

D x :

x D :

[ ]

(

7.2 Operators

page: 9

Linear Operators:

Almost all operators encountered in quantum mechanics are linear operators.

Definition: A linear operator has to satisfy the following two conditions:

( f + g)= A

f +A

g

A

(af ) = aA

f

A

(7.2.9)

Examples:

1) D is a linear operator:

d

df ( x) dg ( x)

g (x )

D ( f ( x) + g ( x ) ) = ( f ( x) + g ( x ) ) =

+

= D f ( x) + D

dx

dx

dx

(af ( x ) ) = d (af ( x ) ) = a df ( x ) = a D f ( x)

and D

dx

dx

2)

S ( f ( x) + g ( x ) ) = ( f ( x ) + g ( x) )2 = f 2 ( x) + 2 f ( x) g ( x) + g 2 ( x ) f 2 ( x ) + g 2 ( x)

(af ( x ) ) = (af ( x) )2 = a 2 f 2 ( x) a S f ( x)

and S

(German: eigen = own, characteristic, individual, belonging to, specific, inherent!)

f = af the functions f are called eigenfunctions of the operator A

, which scale the functions

For A

by the eigenvalues a.

f = af

A

operator

eigenfunction

eigenvalue

(7.2.10)

eigenfunction

on f

In other words: An eigenfunction of an operator A

gives f again, times a constant, the eigenvalue, a.

is a linear operator with an eigenfunction g (and eigenvalue b) , then any multiple of g is also an

If A

.

eigenfunction of A

(7.2.11)

g = bg then A

(cg )

Proof: A

( 7. 2. 9 )

g = cb g = dg

cA

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

7.2 Operators

page: 10

d ax

Example: exp( ax ) = e ax is eigenfunction of D because

e = a e ax

dx

2

2

d ax 2

( e ax is not an eigenfunction, because

e

= 2ax e ax ).

dx

they are called m-fold degenerate.

(7.2.12)

Deduction:

Any linear combination of a set of degenerate eigenfunctions is also an eigenfunction.

Proof:

having the

= a for n = 1, 2, ...m . Hence, this state is m-fold degenerate.

A

n

same

eigenvalue

a.

m

cn n

n =1

g =A

c n n =

n =1

n =1

= a

cn A

n

{

a n

cn n = ag

n =1

qed!

Physical meaning:

If a system is in an eigenstate of observable A (i.e., when the wavefunction is an eigenfunction of the

) then the expectation value of A is the eigenvalue of the wavefunction.

operator A

A function g (which is no eigenfunction) can be expanded in terms of eigenfunctions n of an

(A

= a ):

operator A

n

g=

c

n

(7.2.13)

The new function g is a linear combination of eigenfunctions with the combination coefficients c n

(which might be complex!). (in mathematical terms: The eigenfunctions of an operator form a

complete set, from which other functions can be build up)

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

7.2 Operators

page: 11

From this we can deduce the effect of an operator A

the eigenfunctions n :

g

A

( 7 .2 .13 )

c = c A = c{a = b

n

n n

bn

= g~

Hence this generates another function g~ , which also is a linear combination of the eigenfunctions;

however with different coefficients.

A special case is given we use linear combinations of degenerate eigenfunctions (see chapter

11.4):

Definitions:

1) Orthogonality:

Two functions n and m are orthogonal if the integral over all space (V) is zero.

*

m n

dV = 0

(7.2.14)

2) Normalisation:

A function n is normalised if the integral over all space (V) is one.

*n n dV = 1

(7.2.15)

3) Orthonormality:

If both properties are fulfilled, the functions are called orthonormal.

0 if n m

*m n dV = nm =

1 if n = m

(7.2.16)

7.2 Operators

page: 12

7.2.5 Hermiticity:

Definition of Hermiticity:

is called hermitian, if it fulfils

An operator A

dV = * A

*m A

n

n m dV =

* * dV =

nA

m

* dV

n A

m

(7.2.17)

Deduction:

A hermitian operator has real eigenvalues

(7.2.18)

is assumed to be hermitian. 1) A

= a

A

* * = a * *

2) A

On 1) we operate with * from the left side and on 2) with from the left,too:

= * a = a *

1) * A

* * = a * * = a * * = a * *

2) A

we can integrate over all space or simply recognise, that the left sides of 1) and 2) are identical

was assumed to be hermitian. Hence the right sides must be

(definition of hermiticity) because A

identical, which they are only when a * = a , which is only fulfilled when a is real (qed!).

Physical importance:

All observables (real numbers) correspond to hermitian operators, but -of course- not all hermitians

to observables. (see also expectation values)

(7.2.19)

Deduction:

Eigenfunctions corresponding to different eigenvalues of hermitian operators are orthogonal.

=a

Given: A

n

n n

A

2) A

1)

*

m

*

n

and

dV = a

=a

A

m

m m

dV = a

with a n am and a n , am

dV = *m a n n dV = an *m n dV

*

n m m

*

n

dV

IR

7.2 Operators

page: 13

*

*

*

dV * A

*m A

n

n m dV = a n m n dV am n m dV

to be hermitian, the two terms on the left side are identical, hence:

Because we have assumed A

a n *m n dV a*m n *m dV = an a *m

) *m n dV

= 0

Because A

m

m

n

difference of the eigenvalues is always different from zero and it follows

was to prove (qed!).

*

m n

dV = 0 , which

7.2.6 Commutators:

The key feature of operators -and the reason why they are used in quantum mechanics- is the fact

that they do not generally commute (as we will later see with the uncertainty principle). Another

approach -originally proposed by Heisenberg- used matrices, which do not commute either.

Because of this it is useful to introduce a quantity which expresses this essential property. It is called

the commutator operator [ , ] and defined as follows:

Definition of commutator operator:

,B ] A

B

B

A

[A

(7.2.20)

Notation:

B ] = 0 it is said that A

and B commute!

If [ A,

B ] 0 it is said that A

and B do not commute!

If [ A,

( example above)

Commutator algebra:

,A

] = 0

[A

(7.2.21)

,B

] = [B

,A

]

[A

(7.2.22)

, bB ] = b [ A

,B

]

[A

(7.2.23)

,B

C ] = A

B

C

B

C

A

=A

B

C

B C

A

B

A

C

+B

A

C

[A

B

C

B

A

C

+B

A

C

B

C

A

=A

)

(7.2.24)

+B

]

,B

]C

[A

,C

= [A

B , C

] = [A

,C

]B

+A

[B , C

]

[A

(7.2.25)

7.2 Operators

) (

page: 14

,B

+C

]= A

B + C

B + C A

=A

B + A

C

B

A

C

A = [ A

,B

] + [A

,C

]

[A

(7.2.26)

+ B , C

] = [A

,C

] + [A

,B

]

[A

(7.2.27)

The following table gives a list of typical observables in their classical definition and the

corresponding operators

observable

classical

QM-operator

r = ( x, y , z )

r = (x , y , z ) = ( x, y, z )

x

px

t

y

p = p y = mr& = m

t

p

z

z

t

p x

x

h

=

p = p y = ih =

y

i

p

z

z

position r = ( x, y , z )

linear momentum

p = px , p y , pz

angular momentum

L = Lx , Ly , Lz

Lx

L = Ly = r p

L

z

1

p 2 + p 2y + p z2

2m x

kinetic energy, K

K=

potential energy, U

U(x,y,z), e.g. U ( x) =

total energy, E

L x

L = L y =

Lz

E=K+U

k 2

x

2

y z

y p z z p y

z

y

h

z p x x p z = z x

i

z

x p y p

x y

x

y

x

y

h2 2

h 2 2

2

2

K =

=

+

+

2m

2m x 2 y 2 z 2

= U ( r ) e.g. U = k r 2

U

2

2

h 2

H =

+U

2m

sin cot cos

L x

h

h

where L z = i is to remember!

Lz

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

7.3

7.3 Postulates

page: 15

The postulates cannot be proven. They are axioms of quantum mechanics. However, they are

plausible in the context of defining a fixed framework (mathematical rigorous and without

contradiction) for the description of quantum systems.

Note that different authors very often use different formulations and orders of these postulates!

POSTULATE 1:

1a) Wavefunction:

The state of a physical system is fully described by the wavefunction (=state function):

( r1 , r 2 ,...; t )

with r1, r2,... as the co-ordinates of particle 1, 2, ... and time t.

In this lecture we will deal exclusively with single particles and time-independent problems,

hence the wavefunction simplifies to:

(r )

(7.3.1)

1b) There is a probabilistic interpretation (Born-Hypothesis) to the wavefunction:

The amplitude of (x) is related to the probability of finding the particle at x. The amplitude is

given by *, thus the probability P(r)dr of finding the particle in the volume dr is

P(r ) d r *(r ) ( r ) d r

(7.3.2)

Normalisation condition:

* ( r ) ( r ) d r 1

Comment: However it is customary to also normalise many-particle wavefunctions to 1.

(7.3.3)

7.3 Postulates

page: 16

POSTULATE 2:

2a) A specific state of a system, in which a physical observable A has one specific value a,

, of which then

must be described by (at least) one eigenfunction n to the operator A

an is an eigenvalue.

= a

A

n

n

(7.3.4)

) the

Hence, in any physical measurement of the observable A (associated with operator A

only values that will ever be observed are the eigenvalues a, which satisfy eq. (7.3.4).

A particular and extremely important case is the Schrdinger equation, which

corresponds to the total energy as the observable. (cf. heuristic derivation)

in

2b) Every (classical) physical observable corresponds to a linear hermitian operator A

quantum mechanics, because it must yield real eigenvalues!

(7.3.5)

(see 7.2.5 and 7.2.7)

This postulate captures the central point of quantum mechanics: The values of dynamical variables

can be quantized!

with eigenvalue a, then any measurement of the

If the system is a state, which is an eigenstate of A

quantity A will result in value a.

Although measurements must always yield an eigenvalue, the state doesnt have to be an eigenstate

.

of A

(see

An arbitrary state g can be expanded in a complete set of eigenfunctions (or eigenvectors) of A

linear combinations in 7.2.3).

=a

Hence,

i with A

i

i i

n

g=

c

i

(7.3.6)

where n may go to infinity. In this case we only know that the measurement of A will yield one of the

values ai, but we do not know which one in particular. However, we do know the probability that

eigenvalue am will occur. It is the squared magnitude of the coefficient c m

7.3 Postulates

page: 17

POSTULATE 3:

When a system is described by a wavefunction , the mean value of the observable A is equal to

of the corresponding operator A

. The expectation value is defined as

the expectation value A

A dV

*

dV

*

or for normalised wavefunctions: A

(7.3.7)

A dV

*

(7.3.8)

Deductions:

When m is an eigenfunction of the operator A

A), the determination of A always yields one result, the eigenvalue am.

(7.3.9)

, a single measurement of A yields a single result, which is

When is not an eigenfunction of A

. The probability that a particular eigenvalue am is measured is

one of the eigenvalues am of A

2

Proof of Deduction (7.3.9):

(A

= a ) and is normalised then

If is eigenfunction to A

=

A

A dV = a dV = a dV = a

*

Now the system is considered to be in no eigenstate, but rather in a state expressed by a linear

= a

combination of eigenfunctions: =

c n n with A

n

n n

=

A

=

c A

c dV =

dV

c *m cn *m A

m

m

n

n

n

m n

m

n

c*m cn *m a n n dV

m

c*m cn an *m n dV

m

In a way it only makes sense to consider A

expectation value of a (physical, real) observable. Then the eigenfunctions m and n are

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

7.3 Postulates

page: 18

orthogonal (deduction 2b) and cancel for all n m . In other words, only the terms with n = m

remain. If we further assume normalised wavefunctions, we yield

c*m cm am *m m dV = c*m cm am = cm 2 am

=

A

This is a sum of eigenvalues for that state, weighted by the square magnitude of the combination

coefficients of the probing wavefunction.

Example: Assume a wavefunction which is a linear combination of two eigenstates

with the (real) eigenvalues a and b. Hence,

(eigenfunctions) of the linear, hermitian operator A

= a and A

= b . Calculate the expectation value of A:

= c a a + cb b where A

a

a

b

b

[c + c ] A [c + c ]dV

+c A

] dV = [c + c ] [c a + c b ] dV

= [c + c ] [c A

= ac c dV + bc c dV + ac c dV + bc c dV

14243

142

14243

14243

4 43

4

= *A

dV =

A

a a

*

a a

*

a

b b

*

a b

=1 (normal.)

*

a b

*

b a

= 0 ( 7 .2 .19 )

*

b

= 0 ( 7. 2. 19 )

*

b b

*

b b

=1 (normal.)

= a ca 2 + b cb 2

The average (or expectation) value of the observable A is a weighted average of eigenvalues, where

the weights correspond to the square of the coefficients of the eigenfunctions the wavefunction is

composed from.

Tools:

=

If the mean value of A is defined by A

A dV

*

2

Consequently the mean value of A2 is defined by A

A dV

*

(A A )

(A A ) dV = (A A )(A A ) dV

= (A

A )(A A ) dV = A A A A A + A

= A

2 A A + A dV

= A

dV 2 A A dV + A dV

2

dV

(7.3.11)

( )

2 2 A

2+ A

2 = A

2 A

2 A

A

2

= A

rootThe last definitions are common and useful ! A

mean-square-deviation operator or rms-operator.

7.3 Postulates

page: 19

The central equation of quantum mechanics has to be accepted as a postulate as well! However, you

can find some plausible and heuristic arguments in an attachment

POSTULATE 4:

The wavefunction or state function of a system evolves in time according to the

time-dependent Schrdinger-equation:

(r , t ) = ih (r , t )

H

t

(7.3.12)

However, in the following chapters we will exclusively work with time-independent systems, for

which the time-independent Schrdinger-equation has been already introduced in postulate 2 eq.

(7.3.4):

time-independent Schrdinger-equation:

2

h

(r , t ) =

( r , t ) = E ( r , t )

2 ( r , t ) + U

H

2m

(7.3.13)

Comment:

These are the postulates to an extend necessary to understand the course. Other postulates e.g.

concerning the symmetry of the wavefunction or alternatively the Pauli-exclusion principle may be

defined.

page: 20

We start with the one-dimensional classical wave equation,

2u

x 2

1 2u

(1)

v 2 t 2

we obtain

2 ( x)

f (t )

x 2

( x) 2 f ( t )

v2

t 2

(2)

If we introduce one of the standard wave equation solutions for f (t ) such as exp( it ) (the constant

can be taken care of later in the normalisation), we obtain

d 2 ( x )

dx 2

v2

( x)

(3)

Now we have an ordinary differential equation describing the spatial amplitude of the matter wave as

a function of position. The energy of a particle is the sum of kinetic and potential parts

E =

p2

+ U (x )

2m

(4)

p = 2 m( E U ( x ) )

(5)

Now we can use de Broglies formula to get an expression for the wavelength

=

h

=

p

h

2m( E U ( x) )

(6)

The term 2 /v 2 in equation (3) can be rewritten in terms of if we recall that = 2 and

= v :

2

v

4 2 2

v

4 2

2

2m(E U ( x) )

h2

(7)

page: 21

When this result is substituted into equation (3) we obtain the famous time-independent

Schrdinger equation

d 2 ( x )

dx 2

2m

h2

(E U ( x) ) ( x)

= 0

(8)

h 2 d 2 ( x )

+ U (x ) (x ) = E (x )

2m dx 2

(9)

This single-particle one-dimensional equation can easily be extended to the case of three dimensions,

where it becomes

h2 2

(r ) + U ( r ) ( r ) = E ( r )

2m

(10)

A two-body problem can also be treated by this equation if the mass m is replaced with a reduced

mass .

It is important to point out that this analogy with the classical wave equation only goes so far. We

cannot, for instance, derive the time-dependent Schrdinger equation in an analogous fashion

(for instance, that equation involves the partial first derivative with respect to time instead of the

partial second derivative). In fact, Schrdinger presented his time-independent equation first, and

then went back and postulated the more general time-dependent equation.

page: 22

We are now ready to consider the time-dependent Schrdinger equation. Although we were able to

derive the single-particle time-independent Schrdinger equation starting from the classical wave

equation and the de Broglie relation, the time-dependent Schrdinger equation cannot be derived

using elementary methods and is generally given as a postulate of quantum mechanics. It is possible

to show that the time-dependent equation is at least reasonable if not derivable, but the arguments

are rather involved

The single-particle three-dimensional time-dependent Schrdinger equation is

ih

2 ( r , t )

t 2

h2 2

=

( r , t ) + U (r ) ( r , t )

2m

(11)

where U is assumed to be a real function and represents the potential energy of the system. Wave

Mechanics is the branch of quantum mechanics with eq. (11) as its dynamical law. Note that

equation (11) does not yet account for spin or relativistic effects.

Of course the time-dependent equation can be used to derive the time-independent equation. If we

write the wavefunction as a product of spatial and temporal terms, (r , t ) = ( r ) f (t ) , then eq.

(11) becomes

h2 2

= f (t )

+ U ( r ) ( r )

2m

(12)

ih 2 f ( t )

1 h2 2

=

+

U

(

r

)

( r )

f (t ) t 2

(r ) 2m

(13)

(r ) i h

or

2 f (t )

t 2

Since the left-hand side is a function of f(t) only and the right hand side is a function of r only, the

two sides must equal a constant. If we tentatively designate this constant E (since the right-hand side

clearly must have the dimensions of energy), then we extract two ordinary differential equations,

namely

1 d 2 f (t )

iE

=

2

f (t ) dt

h

and

h2 2

(r ) + U ( r ) ( r ) = E ( r )

2m

(14)

(15)

The latter equation is once again the time-independent Schrdinger equation. The former

equation is easily solved to yield

page: 23

Et

f (t ) = exp i

h

(16)

The Hamiltonian in eq. (15) is a Hermitian operator, and the eigenvalues of a Hermitian operator

must be real, so E is real. This means that the solutions f(t) are purely oscillatory, since f(t) never

changes in magnitude (recall Euler's formula e i = cos i sin ). Thus if

Et

(r , t ) = ( r ) exp i

h

(17)

then the total wave function (r , t ) differs from (r ) only by a phase factor of constant magnitude.

There are some interesting consequences of this. First of all, the quantity (r , t )

is time

Et

Et

(r , t ) 2 = * (r , t ) ( r , t ) = * ( r ) exp i (r ) exp i = * ( r ) ( r )

h

h

(18)

Secondly, the expectation value for any time-independent operator is also time-independent, if

(r , t ) satisfies eq. (17). By the same reasoning applied above,

=

A

( r , t ) dV =

*( r , t) A

(r ) dV

* (r ) A

(19)

For these reasons, wave functions of the form (17) are called stationary states. The state (r , t ) is

stationary, but the particle it describes is not!

Of course eq. (17) represents a particular solution to eq. (11). The general solution to eq. (11) will

be a linear combination of these particular solutions, i.e.

(r , t ) =

E jt

c j j ( r ) exp i

(20)

page: 24

The uncertainty principle (or better: principle of indeterminacy) is NOT strictly a postulate!

A typical (but weak) definition is:

Denies the ability to determine simultaneously and with arbitrarily high precision, the values of

particular pairs of observables, named complementary variables. (e.g. position and linear

momentum):

h

p x x

(7.4.1)

2

=

where A

2 A

2 defines the uncertainty of the observables (specifically the root mean

A

Why is this a weak definition? We still do not know what observables are complementary and why

their uncertainty is h / 2 .

Can one measure an eigenvalue/observable precisely? What are the conditions for this?

state a:

when A is measured, one determines precisely a.

state b:

when B is measured, one determines precisely b.

Deduction:

(7.4.2)

If two eigenstates are to have simultaneously precisely defined values, their corresponding operators

B

= B A

or using definition (7.2.20): [ A

,B

]= 0

must commute. That is A

= a and B = b or is simultaneously eigenfunction to A

and B .

eigenstates: A

B

= A

b = bA

= ba = ab = aB = B

a = B

A

hence, A

B

= B A

or A

B

B A

=0

and A

But what we have deduced so far is only the necessary condition. We have not proven the

B

B A

= 0 implies that A

and B have the same eigenfunction. Or if

sufficient part. This is A

= a is also eigenfunction to B for A

B

B A

=0?

A

= a , then B A

= B a = aB

Given: A

page: 25

B

= B A

we can rewrite:

because of A

= A

B

= aB

B A

( ) ( )

B

= a B

A

when compared with A

fulfilled. If we name the proportionality constant b or B = b , we have proven the claim.

Since we have not made any specific reference in our proof, this is true for all linear operators!

Note: For simplification we have been not really mathematically rigorous. The exact proof it is necessary that

is member

of a complete set and non-degenerate. Otherwise linear combinations of B

condition.

Now we can appreciate the importance of operators, the fact that they do not generally commute

and why a commutator was defined!!

For a more general description of the uncertainty principle, we want to investigate now the case,

that the two operators do not commute and suppose this property in the most general form:

,B

] = iC

[A

Furthermore, the system is in an arbitrary state described by , which is not necessarily an

or B .

eigenfunction ofA

When we measure the system, we get

=

dV

A

* A

=

B

and

B dV

*

but we are more interested in the spread of values around each of these mean values (or in other

words, how broad the values are distributed, or how certain the measurement is). Hence, we use

another deviation operator

B

A

and b = B

a A

and calculate its commutator:

A

,B

B

]= A

A

B B

B B

[ a , b ] = [ A

B B

A

A

B

+ A

= A

)( ) ( )(A A )

A

A

B

B A

+ A

B

)

B ) (B

B

B

A

= [A

,B

] = iC

=A

and B be hermitian, hence a and b

Because we are only interested in real outcomes, we let A

are also hermitian and we define an integral

I=

(a ib )

) (

2

dV where a i b = a * +i b * * a ib

with as a real but arbitrary parameter. This integral relates the two deviations and measures how

much a is different from b (via ) and it is always greater then zero (because of the square).

I=

(a ib )

dV =

page: 26

= * (a + ib )(a ib )dV = * [ a + b ia b + i b a ] dV

I=

= 2 a 2 + b 2 i [ a , b ] = 2 a 2 + b 2 + C

2

2

C

C

+ b 2

I = a 2 +

0

2

2

2

a

4

This statement is true for all real , but we are searching for the minimum deviation (minimal

uncertainty). Because only scales the first term, the minimum is for this term to vanish or

C

=

.

2

2 a

2

The minimum deviation is hence found for b

2

C

4 a 2

a 2 b 2

A

Because a A

1 2

C

4

( )

A

2 = A

2 A

2 A

A

2

, a 2 = A

(A )2 (B )2

1 2

C

4

B

1 C

A

2

This is a more general form of the uncertainty principle!

and B is different from zero,

When the commutator of two operators A

,B

] = iC

[A

(7.4.3)

the observables to these operators are complementary. and hence cannot be determined with

arbitrary precision. The highest precision that can be achieved is then given by:

B

1 C

A

2

=

where A

2 A

2 defines the uncertainty of the observables.

A

(7.4.4)

page: 27

Examples:

1) Calculate the uncertainty of space and associated linear momentum (e.g. in x-direction):

h

h

h

h h

h

[ x , p x ] = x

x =x

x

= = ih

i x

i x

i x

i x i

i

h

= h and we directly get eq. (7.4.1): p x

hence C

x

2

2) Now calculate the uncertainty of spatial observable y and linear momentum in

h

h

h

h h

x-direction: [ y ,p x ] = y

y =y

y

=0

i x

i x

i x

i x i

Hence, we can determine both simultaneously and precise. The two operators commute and are

therefore not complementary!

page: 28

In this optional chapter a very elegant and simple notation is introduced. However, it will be NOT

USED in following chapters to avoid confusion. This part should simply provide you with the

necessary definitions, so that you are enabled to read quantum mechanical literature which often uses

this type of notation.

Diracs bracket notation is an abbreviation for the typical integrals in quantum mechanics and we will

see that may postulates can be expressed in a more handy and short style.

The basic definition is:

n

mA

dV

*m A

n

(7.5.1)

where the symbol n is called a ket and denotes the state expressed by wavefunction n . The

complex conjugate of the wavefunction *n is denoted by the bra n .

When bras and kets are strung together with an operator between them, like as in the bracket

n the integral of eq. (7.5.1) is to be understood. When the operator is simply multiplication

mA

by 1 (or I ) the operator is omitted from the bracket.

Hence the following conditions from the previous postulates become in bracket notation:

normalisation condition:

n n =1

(7.5.2)

orthonormality condition:

n m = nm

(7.5.3)

hermiticity:

n = nA

m*

mA

(7.5.4)

page: 29

Confined particles:

Solutions

To know:

1. Solutions for particle in 1D box

n =

2

a

nx

sin

,

a

En =

n2 h2

8ma

, n = 1, 2, 3, K

3. Separation of variables (approach to 2D/3D problems)

4. Degeneracy

To know:

General recipe for solving QM-problems

1. Determine potential energy

2. Determine boundary conditions

3. Find suitable co-ordinate system

4. Try to separate Schrdinger equation

5. Solve differential equation

6. Determine constants/quantum numbers via boundary

conditions, normalisation, zero-point energy.

8 Confined Particles

8.

page: 30

Confined Particles

Mechanical analogy: Vibrating string, see [1] page 554ff.

U(x)

h2 d2

H = + U (x )

2m d x 2

(8.1.1a)

0 for 0 x a

U (x ) =

(8.1.1b)

for x < 0 and x > a

The particle cannot penetrate the infinitely high potentials at x = 0 and x = a. Therefore, the

wavefunction is only non-zero for the region defined by U(x) = 0, resulting in the Hamiltonian we

already know for free translational motion. The Schrdinger equation is then

with:

d2

dx

2mE

h2

(8.1.2)

(8.1.3)

Considering the boundary conditions (0) = (a) = 0 one gets (0) = A = 0 and

(a) = B sin(ka) = 0. The only non-trivial (particle actually exists) solution is ka being an integer

multiple of .

k=

n

, n 1, 2, 3, K

a

(8.1.4)

En =

n2 h 2 2

2ma 2

n2 h2

8ma 2

, n = 1, 2, 3, K

(8.1.5)

To complete the problem, only B remains to be determined. This is done by normalising the

problem. Because the probability to find the particle in the box must be unity, one simply has to solve

the following equation:

8 Confined Particles

a

*n ( x ) n ( x)

dx =

sin

( )d x = [

2 nx

a

B2 x

2

( )]

a

a

sin 2 n x

4n

a

0

page: 31

B2a

=

2

(8.1.6)

En [8ma 2 /h 2 ]

n =

2

a

sin

nx

,

a

En =

n2 h2

8ma 2

, n = 1, 2, 3, K

(8.1.7)

yn*(x ) yn (x )

yn(x)

n=4

n=3

n=2

n=1

Fig. 8.2: 1D-confined particle: Graphical representation of the wavefunctions (left) and the probability

densities (right) versus the energy of the state for n = 1, 2, 3 and 4.

8 Confined Particles

page: 32

The particle is now confined in a rectangular well with linear dimensions a1 and a2 as depicted in Fig.

8.3. The mechanical analogy to this problem would be a vibrating rectangular drum or sheet, whose

edges are fixed.

U(x,y)

a1

a2

0

0

Fig. 8.3: Geometry of the rectangular well. Note the graphical necessity to give infinity a value!

h2

H =

2m

2

2

+

x 2 y 2

+ U ( x, y)

0 for 0 x a1 and 0 y a 2

U ( x, y ) =

for all other

Hence the Schrdinger equation is (cf. argument above (8.1.4)):

with:

2 ( x, y )

x 2

2 ( x , y )

y 2

2mE

h2

( x, y)

(8.2.1a)

(8.2.1b)

(8.2.2)

This partial differential equation can only be solved if we can separate the variables ( see

excursus E1). We now substitute (8.2.2) with y(x,y) = X(x)Y(y) and divide by XY as shown in

excursus E1:

X X + Y Y = 2mE h 2

(8.2.3)

8 Confined Particles

page: 33

Each term must be a constant summing up to the energy term, which we therefore separate as well

E = EX + EY. So (8.2.3) can be separated into two similar parts:

X ( x) =

2mE X

h

X ( x)

and

2mEY

Y ( y ) =

Y ( y)

with E X + E Y E

(8.2.4)

Each of these equations has the form of (8.1.2) for the 1D-problem and even the boundary

conditions are the same! So we can readily write the solution as:

n x n y

2

sin 1 sin 2

a1 a 2

a1 a 2

n1 , n 2 = X n 1 ( x) Yn 2 ( y) =

n12

a2

1

h

En 1 , n 2 = EnX + E Yn =

1

2

8m

a)

n 22

a 22

(8.2.5)

b)

n2

n1

1

2

c)

y

a2

d)

x

a1

Fig. 8.4: Wavefunctions for a 2D well with a 2 = 2 a 1: a) y11, b) y12, c) y11, d) matrix with grey

shaded pictures for n 1,n 2 = 1,2,3,4. Dark colours represent negative values, bright colours

positive values.

8 Confined Particles

page: 34

A typical feature of 2D/3D systems becomes apparent when the box is geometrically square (cube

for 3D, see Fig. 8.6), that is a1 = a2 = a. Then the energies are

En 1 , n 2 =

h2

8m a

(n12 + n 22 )

(8.2.6)

That means that yab and yba have exactly the same energy, although the wavefunctions are different.

The property of different states having the same energy is called degeneracy, and the corresponding

states to this energy are said to be degenerate.

The wavefunctions of degenerate states typically can be transformed by simple geometrical

transformation (like 90 rotations). Thus, degeneracy can always be traced to an aspect of the

systems symmetry.

8 Confined Particles

page: 35

Don Eigler and co-workers [2] used the tip of a scanning tunnelling microscope (STM) to place

iron atoms on a copper surface (cf. Fig. 8.5a). After finishing the construction of such quantum

corrals they used the same instrument in a different mode to scan the surface, which exhibited

probability distributions of a trapped electron.

a)

b)

c)

Fig. 8.5: STM measurements of quantum corrals: a) Different stages in the assembly of a round

corral, b) the finished round quantum corral with a diameter of 143 , c) a rectangular corral.

8 Confined Particles

page: 36

We have now all tools to solve the 3D Schrdinger equation

h2 2

( x, y, z ) + U ( x , y , z ) ( x, y , z ) = E ( x, y, z )

2m

(8.3.1)

0 for 0 x a1 and

U ( x, y, z ) =

for all other

0 y a2

and

0 z a3

(8.3.2)

Normalised solution for a particle confined in a 3D potential well:

n1 , n 2 , n 3 ( x, y , z ) =

En1 , n 2 , n 3

n x n y n z

8

sin 1 sin 2 sin 3

a1a 2 a3

a1 a 2 a3

=

+

+

8m a12 a22 a32

(8.3.3)

with n1 , n2 , n3 = 1, 2, 3, K

Problem 8.1: Find degenerate states in Fig. 8.4d. Can you tell by looking at the displayed

probability density? Find other states for n1,n2 > 4!

Problem 8.2: Assuming the rectangular corral in Fig. 8.5.c was scanned at 4.2K and contains a

single electron, can you estimate the distance of the iron atoms using eq. (8.2.5)?

Discuss how realistic your result is and what assumptions might be wrong!

Thermal energy E = k BT.

Comparing the thermal and QM energy one can work out the distance of the STM

tip, assuming a particle in a 3D box.

Problem 8.3: How degenerate is (5,6,7) for a particle in a cubic box? (It is not 6)

References:

1.

2.

Mary L. Boas: Mathematical Methods in the Physical Sciences 2nd ed., Wiley,

New York 1983.

M. F. Crommie, C. P. Lutz, D. M. Eigler: Confinement of electrons to quantum

corrals on a metal surface, Science 262(5131) (1993) 218-220; M. F. Crommie, C.

P. Lutz, D. M. Eigler and E. J. Heller, Physica D 83 (1995) 98-108.

8 Confined Particles

page: 37

Fig. 8.6: The first energy levels of a partic le in a cubical box with a 1 = a 2 = a 3 = a together with the

quantum numbers n 1, n 2, n 3 of the corresponding wavefunctions and the degeneracy of each

energy level. The ground state energy is E0 = E111 = 3h 2/(8ma2).

Excursus 1

E1

page: 38

2

2

2

2 ( x , y , z ) = 0 with the Laplacian Operator

2 + +

x 2 y 2 z 2

(E1.1)

However, we want to restrict it to two dimensions for the moment and try a solution of independent

variables, that is:

( x, y ) = X ( x ) Y ( y)

(E1.2)

Y ( y)

d 2 X (x )

dx 2

+ X (x )

d 2Y ( y )

dy 2

=0

(E1.3)

Note that we can write this now in ordinary rather than partial derivatives, because X depends only

on x and Y on y!

We now divide (E1.3) by XY to separate the terms:

1 d 2 X (x )

2

X (x )

x4

1442d4

3

depends on x only

1 d 2Y ( y )

Y ( y ) dy 2

14

4244

3

=0

(E1.4)

depends on y only

1 d 2 X (x )

1 d 2Y ( y )

=

= k2

2

2

X ( x ) dx

Y ( y ) dy

or

X = k 2 X

with k 0

and Y = k 2 Y

(E1.5)

(E1.6)

The constant k 2 is called the separation constant and (E1.6) has the following solutions:

sin( kx)

X ( x) =

cos( kx)

and

exp( ky)

Y ( y) =

exp( ky)

(E1.7)

The solutions (or linear combinations) of the initial problem are therefore:

e ky sin kx

ky

e

sin kx

( x, y ) = X ( x )Y ( y ) = ky

e cos kx

e ky cos kx

(E1.8)

9.

9.1

Classical description

Detail

page: 39

Classical Description

To know:

1. Potential energy: U = k x 2 with k = m2 = 22 m 2 x2

2

9.2

1D Harmonic Oscillator in QM

Detail (solution of differential equation)

MAPLE exercise

To know:

1. Schrdinger-Equation:

h2 d2

m2 2

( x) +

x ( x) = E ( x)

2m dx 2

2

E = s + 1 h = s + 1 h

2

with s = 0, 1, 2,K

2

s ( ) = N s H s ( ) e 2

with = 2 m h x = m h x

3. Zero-point energy s = 0 E0 = h2

4. Potential tunneling (QM Classical)

5. Correspondence principle

Exercises and workshops

9.3

page: 40

MAPLE exercise

To know:

h2 2

1. Schrdinger-Equation:

(r ) + 22 m 2 r 2 ( r ) = E ( r )

2m

with r = ( x, y, z )

2. Solutions: Energy and quantum numbers*

(sx +

s y + s z + 3 h

2

with s x , s y , s z = 0, 1, 2, 3, K

Es x s y s z =

2

s ( ) = N s H s ( ) e 2

with = 2 m h x = m h x

3. Degeneracy

*for identical oscillation frequencies in all 3 dimensions.

9 Harmonic Oscillator

9.

page: 41

Fig. 9.1 The one-dimensional harmonic oscillator. Displacement from equilibrium (x = 0) is denoted by

x.

The classical equation of motion of a particle with mass m is given by Hookes law (cf. Fig. 9.1):

m&x& = kx

or

(9.1.1)

&x& + 20 x = 0

with k = m02 as the spring constant and 0 the natural frequency. The energy of the system is then E = K + U =

In the turning points x 0 the particle comes to a rest (cf. Fig. 9.2) and thus the kinetic energy K = 0

and the energy is entirely potential

E = U = k x02

2

(9.1.3)

For x 2 > x02 , the kinetic energy is negative, which is classically forbidden.

Fig. 9.2: The potential U(x) of the harmonic oscillator. The turning points of the oscillation are at

x = x0, where U(x0) = E.

For the classical case. the probability PCL(x) of finding the particle in the interval dx around the point

x at any time is

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

9 Harmonic Oscillator

P CL ( x ) d x =

page: 42

dt

= 0 dt

T0

2

(9.1.4)

( )

2

with T0 as the period. Combining eqn. (9.1.2) and (9.1.3) gives dd xt = 20 x02 x 2 and thus

P CL ( x ) =

0 d t

1

=

2 d x

2 x 02 x 2

(9.1.5)

x0

x0

Thus N = 2 and

CL

N

( x) d x =

2

x0

x 02

1

x2 2

x0

P CL ( x ) =

N

dx =

2

x 0

N

arcsin

= 1

x0 x

2

x 02

(9.1.6)

(9.1.7)

9 Harmonic Oscillator

page: 43

U ( x ) = 1 kx 2 = 1 m2 x 2 = 2 2 m 2 x 2

(9.2.1)

h2 d 2

( x) + U ( x) ( x) = E ( x )

2m dx 2

d

dx

(x ) +

8 m

h

[E 2 m x ] ( x) = 0

2

2 2

2E

m

and 2

x

h

h

(9.2.3)

d2

() = ( )

d 2

(9.2.4)

thus (9.2.2) becomes:

(9.2.2)

Note: The presented solution uses operators. Brehm and Mullin provide you with an

alternative way using series expansion (check their pages 244-250).

The left side of equation (9.2.4) naively reminds you of equation a2-b2 = (a+b) (a-b), but be

careful because we are dealing with operators here. So we try:

d

d

+

=

+ ( ) = + 2

d

d

d2

= 2 2 1

d

(9.2.5a)

and analogously

d2

d

d

+ = 2 2 + 1

d

d

d

(9.2.5b)

d

a

+

d

and

a +

d

(9.2.6)

d2

() = a a + + 1 ()

d 2

(9.2.7a)

9 Harmonic Oscillator

d2

( ) = a + a 1 ( )

d 2

page: 44

(9.2.7b)

From this equation or the corresponding formulation of the Schrdinger equation in (9.2.4), which is

then (where l() denotes the wavefunction to the energy term )

a a + ( ) = ( + 1) ( )

(9.2.8a)

a +a ( ) = ( 1) ()

(9.2.8b)

a +a a a + = 2

(9.2.9)

Now we take the Schrdinger equation of (9.2.8b) and operate on both sides with a

a a + a () = ( 1) a ( )

(9.2.10)

(a +a 2)a () = ( 1) a ()

a + a a () = ( 1) a ( ) + 2a ()

(9.2.11)

a + a a () = ( 3) a ( )

This corresponds to the Schrdinger equation (9.2.8) for the energy (eigenvalue) -2, or

a + a ( 2 ) ( ) = ( 3) ( 2 ) ()

(9.2.12)

functions corresponding to energy levels (-4), (-6), .... can be created. For this reason the

operator a is called annihilation operator, because operated on it generates the wavefunction

that corresponds to the next lower energy level. Analogously a + is called creation operator,

because it increases the energy level. The pair a and a + are also called ladder operators.

However, annihilation is more useful at the moment, because we know that the decrease of energy

cannot be continued indefinitely, since kinetic and mean potential energy are positive it cannot

become negative. Therefore, there must be a minimum energy assigned by min. and a applied to

( min ) consequently must give 0: a ( min ) = 0 .

(9.2.13)

We operate on both sides with a + and use eq. (9.2.8b) to set it in relation to the Schrdinger

equation:

0 = a + a ( min ) = ( min 1) ( min )

(9.2.14)

thus, min.= 1. As demonstrated above, can take integer values differing by 2, so we conclude that

= 1, 3, 5, 7, ... or with 2s + 1, where s = 0, 1, 2, 3,... Now we

re-substitute using the definition in (9.2.3):

9 Harmonic Oscillator

E =

h

= s + 1 h = s + 1 h

2

2

2

with s = 0, 1, 2,K

page: 45

(9.2.15)

What is left is the determination of the wavefunction, which is now rather simple. Therefore, we take

the wavefunction corresponding to the lowest energy level and all we have to do is to operate on it

with a+ to get the next higher wavefunction and continuation of this procedure gives us any s we

like. (Note that now s rather then is used as a label.)

( )

s ( ) = N s a +

0 ()

= N s dd dd dd K dd

()

( s times) 0

(9.2.16)

with Ns as a normalisation constant. So all left to determine is 0, from which we know it must

satisfy (9.2.13) or

d

d 0

a 0 = + 0 = 0 or

= d ln 0 = d

0

d

2

0 ( ) = N 0 e 2

(9.2.17)

(9.2.18)

2

2

d

1 () exp = 2 exp

2

2

d

2

= N1 [2] exp

2 ( ) = N 2 4 2 2 exp

2

2

3 ( ) = N 3 8 3 12 exp

2

(9.2.19)

the polynomials in squared brackets are known as the Hermite polynomials H1, H2, H3,... which

are summarised in Table 9.1 together with the normalisation constants Ns, which are obtained by

the requirement

() ( ) d = 1 .

E = s + 12 h = s + 12 h

2

s ( ) = N s H s () e 2

with s = 0, 1, 2, K

with = 2 m h x = m h x

(9.2.15)

(9.2.20)

9 Harmonic Oscillator

page: 46

Table 9.1: Energy levels Es, quadratic normalisation constants N s2 and Hermite polynomials H

for various s

s

Es [J]

H s(x)

N2

h

2

3h

2

1 4m

2

h

5h

2

1 4m

8

h

42 2

7h

2

1 4 m

48

h

83 12

9 h

2

1 4 m

384

h

164 48 2 + 12

11h

2

1

4 m

3840

h

4m

h

2 s s!

2 ds

2

( 1) s e

e

d s

....

s

4 m

h

(s + 12 )h

Exercise 9.1:

H s( y ) 2 y H s (y) + 2 s H s ( y) = 0

(9.2.21)

H s +1 ( y ) + 2 s H s 1 ( y ) 2 y H s ( y ) = 0

(9.2.22)

H s ( y ) = 2s H s 1 ( y )

(9.2.23)

Show that the normalisation constants in Tab. 9.1 are correct! (Use:

exp( a

0

2 2

x ) dx =

for a > 0)

2a

9 Harmonic Oscillator

E [hn]

11/2

9/2

7/2

5/2

3/2

1/2

y(x)

page: 47

y*(x ) y(x )

Fig. 9.3: Graphs of the wavefunctions (left) and probability density functions (right) of the 1D

harmonic oscillator for the first 5 energy levels versus dislocation y. The red curves on the

right represent the probability density functions of the classical harmonic oscillator (cf. eq.

(9.1.7)).

On the right side of Fig. 9.3 we observe, that with increasing energy or s the quantum mechanical

probability density PsQM () is becoming more and more similar to the classical probability density

PCL () (red curves in Fig. 9.3). This observation is further illustrated in Fig. 9.4, where the two

functions are compared for E20 = 21h/2.

9 Harmonic Oscillator

page: 48

P(x)

Fig. 9.4: Illustration of the correspondence principle: Black curve: Quantum mechanical probability

density function of a high energy state (20())2. Red curve: Classical probability density

function from (9.1.7).

The principle that for large quantum numbers (e.g. energies) the quantum mechanical probability

distribution function PQM resembles the classical probability distribution function PCL is called

correspondence principle (see Fig. 9.4), it describes the limiting regime where quantum mechanics

meets classical mechanics (c.f. de Broglie relation).

correspondence principle:

lim PsQM ( r ) = P CL ( r )

dt

dr

In other words, the system behaves only classically, when there is sufficient energy.

Exercise 9.2: Demonstrate the correspondence principle of a particle in a 1D-box.

(9.2.24)

9 Harmonic Oscillator

page: 49

The solution of the 2D harmonic oscillator is omitted (see eq. (8.2.3) and the following treatment

of the 3D harmonic oscillator). The results are:

Es x s y = s x + 1 h x + s y + 1 h y = s x + 1 h x + s y + 1 h y

2

with s x , s y = 0, 1, 2,K

2

2

s x s y ( , ) = N s x s y H s x () e 2 H s y () e 2

(9.3.1)

(9.3.2)

with = 2 m x h x = m x h x

and = 2 m y h y = m y h y

N s2 s =

x y

4m

(s +s )

2 x y sx ! s y ! h

1

x +y

(9.3.3)

quantum numbers

( s x , sy )

degeneracy

(01) (10)

(00)

E/hn

energy

levels

9 Harmonic Oscillator

page: 50

0

Fig. 9.6: Energy diagram for a symmetrical (Ux = Uy = U) two-dimensional harmonic oscillator.

Compare with Fig. 9.7.

s2

s1

0

1

2

3

Fig. 9.7: Wavefunctions for a symmetrical (Ux = Uy = U) two-dimensional harmonic oscillator. Black

for negative, white for positive values. Compare the pattern for the degenerate states from

Fig. 9.6.

9 Harmonic Oscillator

page: 51

Fig. 9.8: The first four wavefunctions with identical quantum numbers (00, 11, 22, 33) for a

symmetric potential. (Note: The states with mixed quantum numbers are not shown and not

both potentials are drawn. The red line is an diagonal average).

9 Harmonic Oscillator

page: 52

U (r ) =

k 2

r = 22 m 2 r 2

2

(9.4.1)

r 2 = x 2 + y2 + z 2

with

(9.4.2)

h2 2

( r ) + 2 2 m 2 r 2 ( r ) = E ( r )

2m

(9.4.3)

and:

2E

2

=

E X + E Y + E Z X + Y + Z

h h

m

x,

h

m

y,

h

m

z

h

(9.4.4)

(9.4.5)

2

2

2

+

+

(, , ) 2 + 2 + 2 (, , ) = ( , , )

2

2

2

(9.4.6)

As in the 2D and 3D treatment of a confined particle in zero potential (cf. chapter 8.2 and 8.3) we

assume the solution to be a product of functions X,Y,Z, which depend on one spatial co-ordinate

only:

(, , ) = X ( ) Y ( ) Z ( )

(9.4.7)

1 dX ( )

2 + X

X ( ) d 2

1 dY ( )

+

2 + Y

Y ( ) d 2

1 dZ ( )

2

Z

+

=0

Z ( ) d 2

(9.4.8)

When each term becomes zero the equation is fulfilled, for instance for the first term:

1 dX ( )

2 + X = 0

2

X ( ) d

dX ()

d

2 X () + X X () = 0

dX ( )

d

(9.4.9)

2 X () = X X ( )

This the same expression as eq. (9.2.4), of which we know the results (eq. (9.2.15) and (9.2.16)).

Hence, the solution of the Schrdinger equation for the 3D harmonic oscillator is given by:

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

9 Harmonic Oscillator

page: 53

(for a symmetrical potential*)

Es x s y s z = s x + 1 h + s y + 1 h + s z + 1 h = s x + s y + s z + 3 h

2

2

2

2

with s x , s y , s z = 0, 1, 2, 3, K

2

2

2

s x s y s z (, , ) = N s x s y s z H s x ( ) e 2 H s y () e 2 H s z ( ) e 2

with = 2 m h x , = 2 m h y , and = 2 m h z

N s2 s s =

x y z

1

2

(s x + s y + s z )

3

4m 2

sx ! s y !sz !

Fig. 9.9: Energy diagram for the first 4 states of a symmetrical 3D harmonic oscillator.

(9.4.10)

(9.4.11)

(9.4.12)

(9.4.13)

page: 54

10.1/2

Detail

Classical Description

To know:

1. Linear / Rotational Motion:

2. Reduced Mass

3. Boundary Conditions

Detail (Co-ordinate transform)

To know:

1. Schrdinger-Equation in circular co-ordinates

2. Solutions and quantum numbers

1

e im

2

m ( ) =

Em = m

2 h

2I

and

with m = 0, 1, 2, 3, K

Lm

z = mh

3. Uncertainty and m = 0

4. Shape of wavefunctions, auxiliary functions, Lz

page: 55

Detail (Co-ordinate transform)

MAPLE exercise

To know:

1. Schrdinger-Equation in spherical co-ordinates.

2. Integration limits for spherical co-ordinates.

3. Solutions (spherical harmonics)*

Schrdinger-eq.

l

l

im

wavefunctions Ym (, ) = N lm Pm (cos ) e

h2

energy El = l (l + 1)

2I

4.

5.

6.

7.

Orbital Shapes (simple ones)*, dependence on l, m

Probability density, ()-dependence

Degeneracy

* not in detail, but their composition and dependence (the most simple you could remember!)

page: 56

Detail

To know:

1. Linear definitions, eg. . L x = y p z z p y = hi y z z y

2

2 2

2. L z = i and L = h

applications to spherical harmonics

3. Spatial quantization: L = h l (l + 1)

10 Rotational Motion

page: 57

10.1 Classical Rotation in a 2D Plane

We remember the classical expressions for linear and rotational motion, as listed in Table 10.1:

Tab.10.1: Classical expressions for linear and rotational motion in a plane

linear motion

rotational motion

co-ordinates

Cartesian: r = x,y

circular: r, f

mass

moment of inertia:

I = mi ri2

i

linear velocity:

v x = x& , v y = y&

angular velocity:

v rv v

=

, = 2

r2

v = r&

momentum

force:

kinetic energy:

linear momentum:

p = mv

L = r p , L = I

linear force:

F = p& = ma

torque:

T = r F = I &

K=

angular momentum:

1 2 p2

mv =

2

2m

K=

1 2 L2

I =

2

2I

The typical case, where we wish to apply the following treatment, is the rotation of a (at least)

diatomic molecule around its centre of mass (Fig. 10.1).

z

L

r0

m

a)

b)

Fig. 10.1: a) Rotation of a diatomic molecule around its centre of mass (CM). b) Without loss of

generality the system can be described by the rotation of a reduced mass m.

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

10 Rotational Motion

page: 58

First we want to reduce the problem to a single mass problem. Since the rotation is around the

centre of mass. In good agreement with nature we can assume point-masses:

m1 r1 = m2 r2

m1 r1 = m2 ( r r1 ) or r1 =

hence:

and r0 = r1 + r2

m2

m1

r0 and r2 =

r

m1 + m2

m1 + m2 0

I = m1r12 + m2 r22

(10.1.1)

(10.1.2)

(10.1.3)

I = m1

m12

m m (m + m1 ) 2

m1 m2

r02 + m2

r02 = 1 2 2

r0 =

r02

2

2

2

(

m

+

m

)

(m1 + m2 )

(m1 + m2 )

(m1 + m2 )

1

2

I = r02

m22

with =

(10.1.4)

m1 m2

as the ' reduced mass '

(m1 + m2 )

Analogously we can reduce the masses of a many-body problem, without loss of generality!

For a simple start, the particle shall be confined on a circular path (e.g. a bead on a circular wire).

Thus moving in zero-potential, and the total energy is kinetic only.

E=K =

p2

L2

L2

=

=

2m

2I

2r02

(10.2.1)

p=

h

hr

or L =

(10.2.2)

The consequence of (10.2.2) is that the angular momentum is inversely proportional to the

wavelength of the particle. Thus, the shorter the wavelength the higher the angular momentum, the

higher the energy. If can take arbitrary values, after one round the particle-wave will have a

different amplitude at the same position. Therefore, the corresponding wavefunction will have

different values at the same position, which is a violation of the first QM-postulate. Hence, only such

are quantum mechanically allowed, which form standing waves on the orbit (see Fig. 10.2). In

other words has to be an integer multiple of the path length:

2r0 = m

(10.2.3)

10 Rotational Motion

page: 59

and finally vanish. We havent specified the quantisation

number m yet. Because the particle can move clock- and

counter-clock wise we allow positive and negative integers.

Like in the case of a particle in a box, we might not allow

m = 0, because this would correspond to zero energy, but

we might reconsider this after a more complete quantum

mechanical treatment.

b) acceptable wavefunctions

we have already found expressions for the quantized energy

of the particle on a ring, the rigid rotator, or

unrestricted motion on a circular path. All left to do is to

combine eqs.(10.2.1)-(10.2.3):

Em =

L2 h 2 r02 h 2 r02 m2

=

=

=

2 I 2 I 2

82 I r02

h2 m 2

with m = 1, 2, 3, K

2I

(10.2.4)

Note: Careful that you do not confuse m with mass. At the moment we might call it the azimuthal

quantum number !!

We do not have to consider a potential, so the Schrdinger equation for the rigid rotator is

formally the same as for the free particle in two-dimensional Cartesian co-ordinates with the

boundary conditions of being constrained to a circular path:

Schrdinger equation for a free particle in 2D

2

2

2 ( x , y ) = ( x , y ) + ( x, y ) = 2mE ( x , y )

x 2

y 2

h2

(10.3.1)

However, Cartesian co-ordinates are not a suitable co-ordinate frame. 2D-polar or circular coordinates are better suited for the problem, because r = r0 is a constant. Therefore we transform eq.

(10.3.1) into circular co-ordinates (r,) (see Excursus 2: eq. (E2.16)) and replace the mass m by

the reduced mass .

10 Rotational Motion

page: 60

The Schrdinger equation for the rigid rotator in circular co-ordinates is therefore:

1 2

1

2E

(r , ) =

(r , )

r ( r, ) + 2

2

r r r

r

h2

2 (r , ) =

(10.3.2)

This looks more complicated then (10.3.1), but since r is not a variable but a constant r0 (supplied

by the rigidity of the rotators axis), it simplifies to (using eq. (10.2.4) to express E as L2 and m,

eq. (10.1.4) for I):

1 d2

r02

d

() =

() =

2E

h2

2Er02

2

h

()

(10.3.3)

() =

L

h

() = m 2 ()

We acknowledge that the partial differentials became ordinary, and that this equation has been

solved already for the free one-dimensional particle (see part 5c of John Dores part). At the

moment we still consider m as unrestricted in value despite our previous considerations.

The solutions to (10.3.3) are (for generality we allow complex solutions):

() = Ae im + Be im

(10.3.4)

() = ( 2 + )

(10.3.5)

Aeim + Be im = Ae im ( 2 + ) + Be im ( 2 + )

Ae

im

+ Be

im

= Ae

im 2

im

+ Be

im 2

im

(10.3.6)

This can only be fulfilled if m is an integer (because e im 2 = 1 for m = 0, 1, 2, ...), which also

satisfies our previous considerations, and the wavefunction reproduces itself on the next circuit.

Energy and angular momentum are quantized.

Since we allow m to have negative and positive integer values, let us compare the cases m and -m in

eq. (10.3.4). Obviously they correspond to the same state when A and B are swapped. The

corresponding energies (Em m 2 ) are the same, so the states are degenerate. However, the

angular momentum L is pointing in opposite directions (+z and -z). Hence, the two states correspond

to rotation in opposite directions. Because the same considerations hold for the wavefunction with

either A = 0 or B = 0, we want to eliminate this unnecessary ambiguity and rewrite eq. (10.3.4) as:

m () = Aeim

(10.3.7)

10 Rotational Motion

page: 61

This also allows the determination of A by normalisation (Note the integration limits for ):

2

* () () d =

0

Hence, A = 1

im

im

d = A

1 d = 2 A

=1

(10.3.8)

and we could readily write down the solution. However, there is still the unsolved

case m = 0! For the discussion of a particle in a box we have used two arguments, as to why the

corresponding state doesnt exist: 1) It wouldnt agree with Heisenbergs uncertainty principle

(since the particle was confined, it has had a finite position range, so the momentum/energy must not

become zero). 2) The corresponding wavefunction (cf. eq. (8.1.7)) would become zero, which

would violate the first postulate.

Lets now consider the same arguments for the case of the rigid rotator. The second can be solved

directly and 0 ( ) = 1 0 . It is constant but not zero, so it exists! The first argument based on

2

the fact, that the particle is confined. Actually it is not, it moves free on its circular path in zero

potential. The idea that it is constrained to the ring originates from the viewpoint of its path in 2DCartesian co-ordinates, but we have solved the problem in circular co-ordinates, and we will find

expressions for its wavefunction for any . (The Schrdinger equation is identical with that of an

unconstrained particle in 1D Cartesian co-ordinates.)

Therefore, we allow m = 0 as an eigenvalue of the Schrdinger equation1.

Normalised solution of the Schrdinger equation for the rigid rotator

m () =

1

e im

2

Em = m 2

h2

2I

with m = 0, 1, 2, 3, K

(10.3.9)

Lmz = mh

(10.3.10)

and

From the solutions we directly observe, that each state is doubly degenerate due to rotation in

opposite directions (Lz pointing up- or downwards) but with the same speed (energy). Except for

m = 0 where Lz is zero and the question of direction doesnt arise.

There are several ways to depict the wavefunctions. A problem arises, because they are complex

e im = cos( m) + i sin( m) . We get somewhat around the problem by plotting the real part only

(since the imaginary is just 90 phase shifted) as done in Fig. 10.3.

The treatment in eq. (10.2.4) might still be treated as correct, because we didnt explicitly consider circular coordinates at that point. However, it has no particular meaning, because we didnt solve the Schrdinger equation

for 2D-Cartesian co-ordinates.

10 Rotational Motion

page: 62

Fig. 10.3:

Graphical representation of the

wavefunction (real part) for the rigid

rotator

(m = 0,1,2,3).

The

wavefunctions for m = -1, -2, -3

look identical, but the direction of

rotation alters (small arrow) and the

angular momentum (bold arrow)

points down.

However, this gives a wrong picture, because it suggests, that the particle is distributed non-uniformly

over the circle. As shown in eq. (10.3.8) the probability distribution is independent of and hence

uniform. Hence, when the particle is in a state of definite angular momentum its distribution is

completely uniform!

A better representation is shown in Fig. 10.4, where an auxiliary function is constructed by

connecting each point of the perimeter to the centre and to mark on this radius a length proportional

to the amplitude of the wavefunction (see Fig. 10.4a). In other words, this is the plot of the amplitude

in polar co-ordinates. Hence, for 0 we would obtain a circle.

This procedure allows us to project the wavefunction into a plane and the overlay of its real and

imaginary part (see Fig. 10.4c and d). The sum of their magnitudes than somehow resembles the

probability distribution (note overlapping parts in Fig. 10.4c/d, they correspond to the gaps from a

circle).

10 Rotational Motion

b)

a)

+

_

+ _

+

_

_

c)

page: 63

d)

Fig. 10.4: a) Construction of the auxiliary function from the real part of 1. b) Same for 2. c)

The auxiliary function from a). Dark colour denotes the real part, brighter grey the

imaginary part. d) Same as c) for 2 or b) respectively.

The assumption, that we can describe rotational motion of molecules

by moving on a circular path is quite naive. Because how should the

molecules in a macroscopic sample know which plane is designated.

Typically there is no preferred direction. Therefore, a description by

rotation on the surface of a sphere is a more likely approximation.

We still assume the molecule to be completely rigid along its bond (r

= r0 = const.). From our experience with other two-dimensional

quantum systems, we expect 2 quantum numbers necessary to

Fig. 10.5:

describe the system, because there are two degrees of freedom in

Schematic representation of

rotation (see Fig. 10.5).

a particle moving on the

surface of a rigid sphere. The

arrows indicate the two

degrees of freedom in

rotation.

10 Rotational Motion

page: 64

Hence, we have to express the Schrdinger equation in 3D polar (spherical) co-ordinates with a

wavefunction that depends on both spherical angles (and the radius), y(r, , ). Fig. 10.6 shows

their interdependence.

Fig. 10.6: Relation between Cartesian and spherical co-ordinates and their range.

In the excursus to this chapter it is shown, how the Laplacian operator is converted into spherical coordinates (see eq. (E2.2.24))

2 =

1 2

1

1

2

r

+

sin +

r 2 sin 2 2

r 2 r r

r 2 sin

Following the same assumptions as in section 10.3, we can directly derive the Schrdinger

equation (r = r0 = const., mass: m ):

1

2

2E

sin ( , ) +

( , ) =

(, ) (10.4.1)

r02 sin

r02 sin 2 2

h2

1

After multiplication with r02 sin 2 and setting r02 = I the equation becomes:

2

2 IE

sin sin (, ) +

( , ) =

sin 2 ( , )

2

2

(10.4.2)

depend on one variable only:

(, ) = ( ) ( )

(10.4.3)

10 Rotational Motion

page: 65

sin d

d

1 d2

2 IE

( ) =

sin 2

sin ( ) +

2

() d

d

() d 2

h

(10.4.4)

We rearrange the terms that depend on or on either side of the equation and substitute the

energy term by 2IEh 2 :

sin d

d

1 d2

2

( )

sin ( ) + sin =

() d

d

( ) d 2

(10.4.5)

To be solvable each side must correspond to a constant! We take a closer look at the right term and

recognise it as identical to eq. (10.3.3) when choosing the separation constant to be m2. So we

have to solve two equations depending on and :

d2

d

and

( ) = m2 ( )

sin d

d

2

2

sin ( ) + sin = m

() d

d

(10.4.6)

(10.4.7)

The first we have already solved in the previous section and can copy its solution from (10.3.9):

m ( ) =

1

e im with m = 0, 1, 2, K

2

(10.4.8)

Equation (10.4.7) however is new and more complicated. First we multiply with ( ) / sin 2 and

rearrange:

1 d

d

m 2

( ) = 0

sin ( ) +

2

sin d

d

sin

(10.4.9)

Now we want to get rid of all the sin terms. Because we have to take its derivative we choose for

substitution a new function

P( ) = cos

(10.4.10)

and with d = sin d and the Pythagoras relation 2 = 1 sin 2 equation (10.4.9) becomes:

d

dP ( )

m2

1 2

+

P ( ) = 0

2

d

d

1

(10.4.11)

10 Rotational Motion

(1 2 )P () 2P () + 1 m 2 P ( ) = 0

2

or

page: 66

(10.4.12)

This type of equation is called associated Legendre differential equation (see e.g. [1] page 504)

with eigenvalues = l ( l + 1) and has solutions Pl m () for l m l and l as an integer called

the associated Legendre functions. They have the following general form of (Legendre) polynomials

of degree l and order m:

( 2)

P m ( ) = ( 1) m 1

m

2

2l l !

l

(

2 1)

d l + m

dl + m

(10.4.13)

and can be normalised by the following integral over the entire range (N as the normalisation

constant):

1

(N P

2

2 ( l + m )!

(

)

d = N 2

=1

l

2l + 1 (l m )!

m

Nlm =

(2l + 1)(l m )!

(10.4.14)

2(l + m )!

(We might derive this solution either by series expansion or by expressing them by the mth derivative

of the Legendre functions Pl(), which can be generated by ladder operators of the type

b + = (1 2 ) d l and b = (1 2 ) d + l , completely analogous to the previous treatment of

d

the harmonic oscillator. However the solution is quite lengthy due to the interdependence of m and l)

We have seen that the dependent part of the Laplacian operator in spherical co-ordinates

produces differential equations of the Legendre type. It is common practice and useful to denote the

part with the angular derivatives of the Laplacian by a new operator, which we will call Legendre

operator (or Legendrian)2:

2 =

1

1 2

sin +

sin

sin 2 2

(10.4.15)

The Legendrian measures the curvature of a function relative to the surface of a sphere. Thus its application to a

wavefunction that represents a sphere is zero, because a sphere in spherical co-ordinates is flat.

10 Rotational Motion

page: 67

2 () () = () ()

We have seen that m ( ) =

with

2IE

h2

( , ) = ( ) ( )

and

(10.4.16)

1

eim with m = 0, 1, 2, K

2

( ) = Pml (cos ) with l m l

(10.4.17)

Because m is limited by l, it is often referred to as ml. As eigenvalues for the associated Legendre

equation we found with the condition that l is an integer:

=

2IE

h2

= l (l + 1) with l = 0, 1, 2, K

(10.4.18)

(, ) = ( ) ( ) =

with l = 0, 1, 2, K and

(2l + 1)(l m )!

4(l + m )!

(10.4.19)

l m l

This lengthy expression is typically abbreviated by (again) new functions Yml ( , ) called spherical

harmonics. We summarise the mathematical treatment:

Particle rotating on a sphere:

Schrdinger equation:

2 Yml (, ) = l ( l + 1) Yml ( , )

Yml ( , ) =

Energy:

El = l (l + 1)

Quantization conditions:

l = 0, 1, 2, K and

(10.4.20)

(2l + 1)(l m )!

4 ( l + m )!

Pml (cos ) e im

h2

2I

l m l

(10.4.21)

(10.4.22)

(10.4.23)

10 Rotational Motion

page: 68

Table 10.2: Composition of the spherical harmonics Yml ( , ) for the quantum numbers

l 3 and -l m +l

l

El *

Pml () **

Pml (cos )

l

Nm

***

cos

1

2

m 1 2

m sin

1

4

1

2

1

2

m 3 1 2

m 3 cos sin

1

12

30

31 2

3 sin 2

1

24

30

12

1

2

12

12

12

(3 2 1)

(

1

2

(3 cos 2 1)

(5 3 3 )

1

( 2 5 sin 2 ) cos

2

m 32 5 cos2 1 sin

1

12

21

15 sin 2 cos

1

120

210

m 15 sin 3

1

120

35

( )

32

m 15(1 2 )

15 1 2

1

4

1

2

m 3 5 2 1 1 2

Yml ( , )

3

4

cos

m 83 sin e i

5

16

(3 cos 2 1)

15

32

sin 2 e i 2

7

( 2 5 sin 2

16

21

64

) cos

(5 cos 2 1)sin ei

105

sin 2 cos e i 2

32

35

sin 3

64

e i 3

* in multiples of h 2 (2 I ) = l(l+1)

** from eq. (10.4.13)

***from eq. (10.4.14)

So far for math, but what do the spherical harmonics look like? We have solved a problem for a

particle on a sphere, and the result is a (sometimes) complex wavefunction on the surface of the

sphere. How can one visualise this? The problem is identical with projecting the globe of the earth

onto a 2D-map! We are used to projections of the earth onto a cylinder, so that the poles become

as large as the equator, although they are points (pseudo Mercator-projectons). In our case the

latitudes correspond to from 0 (south pole) to p (north pole) and the longitudes to from 0

(Greenwich) to 2 (again Greenwich, so UK is at the left and right edge). Although this is a rather

contorted view of reality, you might find it instructive (see Fig. 10.7).

These wavefunctions projected on a sphere are more realistic, but you are restricted to the view on a

single hemisphere (see Fig. 10.8).

Another possibility is to plot auxiliary functions (like in the 2D case, cf. Fig. 10.4), but this time we

will plot the amplitude of the wavefunctions in spherical co-ordinates (see Fig. 10.9). Like in the

2D-case this disables us to distinguish the sign of , but it is a more realistic representation of the

wavefunction. (To understand the relation between Fig. 10.7, 10.8 and 10.9, find the nodes -now

nodal planes- in Fig. 10.7 and mark them on the projections onto a globe, as in Fig. 10.8.

Realise that is spanning the entire diameter, so that nodes separated by -or half the image widths

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

10 Rotational Motion

page: 69

in Fig. 10.7- correspond to the same nodal plane in Fig. 10.8 and 10.9. For a better

comparison switch to graph 10.10, where all three representations are compared next to each

other.)

Finally we want to calculate the probability density function:

QM

Plm

( , ) = Yml * (, ) Yml (, )

lm* () *m ( ) lm ( ) m ( )

(10.4.24)

Consulting eq. (10.4.8) We directly see that *m ( ) m ( ) = 1 and from eq. (10.4.13) that

lm* ( ) = lm ( ) , because lm () is always real. Hence, (10.4.24) becomes:

QM

Plm

( ) = lm ( )

(10.4.25)

We have just proven that the probability density function is (like in the 1D case) homogeneous with

QM

respect to . In other words, Plm

() is not homogeneous with respect to .

QM

Fig. 10.10 shows Plm

() in the three different visualisation modes we have used (map

corresponds to Fig. 10.7, globe to 10.8, aux. to 10.9). Note the similarity of the probability

density functions along the diagonal of Fig. 10.10! The auxiliary functions look almost alike (e.g.

QM

QM

P1QM

1 () P2 2 () P3 3 () ), however they are not identical! They have the same symmetry,

but since they correspond to different energy levels, their curvature along must increase with the

quantum numbers, as it can be clearly seen form the map-graphs! Also note that the nodal planes

now correspond to black colour and since we have taken the square of the wavefunction, we might

no longer consider them as planes but nodal cones (planes are then cones for =/2 and 0)!

The last question we are going to consider is the energy term scheme (see Fig. 10.11) for the

particle on a sphere and the degeneracy of its levels. As shown by eq. (10.4.22), the energy of the

system doesnt depend on m, although m is always spanning a range -l m +l resulting in the

same energy. Hence the degeneracy of each energy level is 2 times l (each m is covering the range of

l twice) +1 (for the zero):

Degeneracy of El

is

2l+1

for l = 0, 1, 2, ....

(10.4.26)

h2

h2

E = El +1 El = [(l + 1)( l + 2) l (l + 1)]

= (l + 1)

2I

I

(10.4.27)

B=

h

4cI

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

(10.4.28)

10 Rotational Motion

Yl m ( , )

m=0

Real

m = +1

Real

Imag

m = -1

Real

Imag

page: 70

m = +2

Real

Imag

m = -2

Real

Imag

m = +3

Real

Imag

m = -3

Real

Imaginar

y

l=0

l=1

l=2

l=3

Fig. 10.7:

Cylindrical projections of the wavefunctions Yl m ( , ) of a particle on a sphere (pseudo Mercator-projections). The vertical axis is from 0 to

, the horizontal axis is from 0 to 2. White colours depict positive and black negative amplitudes. Nodes are in mid-grey! (Note that this is a

rather distorted view of the wavefunctions).

10 Rotational Motion

Yl m ( , )

m=0

Real

l=0

m = +1

Real

Imag

m = -1

Real

Imag

page: 71

m = +2

Real

Imag

m = -2

Real

Imag

m = +3

Real

Imag

m = -3

Real

Imaginar

y

f=0

q=0

l=1

l=2

l=3

Fig. 10.8:

Projections of the wavefunctions from Fig. 10.7 on a sphere. The view is from = 30 and = 270 from 0 to 2 (on the globe of the earth this

would correspond to somewhere over the southern Pacific). White colours depict positive and black negative amplitudes. Nodes are in mid-grey!

Yl m ( , )

m=0

Real

10 Rotational Motion

m = 1

Real

page: 72

m = 2

Imaginary

Real

m = 3

Imaginary

Real

Imaginary

l=0

l=1

l=2

l=3

Fig. 10.9:

Projection of the magnitude of the wavefunctions Yl m ( , ) in spherical co-ordinates, generating a 3D-version of the auxiliary functions as

described in Fig. 10.4.

m=0

QM

Plm

( )

map

l=0

10 Rotational Motion

globe

page: 73

m = 1

aux.

map

globe

m = 2

aux.

map

globe

m = 3

aux.

map

globe

aux.

f=0

q=0

l=1

l=2

l=3

Fig. 10.10: The probability density functions of the particle on a sphere. As shown in eq. (10.4.25) it is only a function of . The three different

visualisations are directly compared. Map corresponds to the pseudo Mercator-projection of Fig. 10.7. Globe is a plot of the wavefunction on

the sphere as in Fig. 10.8, and aux. is the plot of the amplitude in spherical co-ordinates (cf. Fig. 10.9). Note that the levels gray scale now

from 0 to max, so the nodal planes/cones are black!

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

10 Rotational Motion

energy

levels

quantum

number

degeneracy

l=4

12

l=3

l=2

2

0

l=1

l=0

3

1

E

2

[2I/ h ]

20

Fig. 10.11:

l (+1)

l

page: 74

2l+1

Before we finish the chapter, we want to investigate the angular momentum of unrestricted motion on

a sphere, or free 3D rotation. The angular momentum is defined as (see Tab. 10.1)

ex

Lx

x px

L = Ly = r p = y p y = x

L

z p

px

z

z

ey

y

py

yp z zp y

ez

z = zp x xpz

pz

xp y yp x

(10.5.1)

Also from Tab. 10.1 we see that the kinetic energy can be expressed in terms of angular momentum.

Since we didnt have to consider potential energy in section 10.4, we can express the total energy

as kinetic energy.

E =K=

with

L2

2I

(10.5.2)

(10.5.3)

In the context of eigen-equations and the entire context of quantum-mechanics, it is more useful to

express angular momentum Lx, Ly, Lz and L2as operators. The straightforward way is to rewrite

(10.5.1) for each component of L by the operators of position and linear momentum:

L x = y p z z p y = hi y z z y

(10.5.4)

(10.5.5)

L z = x p y y p x = hi x y y x

(10.5.6)

L y = z p x x p z = hi z x x z

10 Rotational Motion

page: 75

As before we rewrite these equations in polar notation, which is more suitable to the problem. From

Fig. 10.6 we get the expressions for the Cartesian co-ordinates:

x = r sin cos

y = r sin sin

z = r cos

(10.5.7)

Hence,

L x = h r sin sin r cos

i

z

y

L = h r cos r sin cos

y

(10.5.8)

Now, we express the partial derivatives of the polar co-ordinates by the Cartesian (you might use

the recipe of E2.2 - the other way around) or work it out:

=

r

x y z

+

+

= sin cos + sin sin + cos

r x r y r z

x

y

z

x y z

+

+

= r cos cos + r cos sin r sin

x y z

x

y

z

x y z

+

+

= r sin sin + r sin cos +

x y z

x

y

(10.5.9)

After some reformulation (for which we do not need r , because L must not depend on r), we

get:

L x = h sin cot cos

i

L y = h cos cot sin

i

L = h

z

(10.5.10)

Check the result by substituting the expressions of (10.5.9) into (10.5.10) and try to derive (10.5.8).

This is easier then the other way around ( cot = cos / sin ).

We are left with deriving an equation for L 2 = L (L ) = L x (L x ) + L y (L y ) + L z (L z ) . When we do

by using the expressions in (10.5.10), this becomes quite lengthy, but try it. The approach here is

different by looking at eq. (10.5.2). If the system has no potential energy (like in section 10.4),

the total energy is purely kinetic and expressed by L2. In operator notation we conclude, that the

following eigen-equation must be valid for L 2 :

L 2 (, ) = 2 IE ( , )

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

(10.5.11)

10 Rotational Motion

page: 76

2 ( , ) =

(, )

h2

(10.5.12)

we find (cf. (10.4.15), the same result we would get using the explicit expressions in (10.5.10)) :

2

1 2

h 1

L 2 = h 2 2 =

sin

i sin

sin 2 2

(10.5.13)

Since we have solved eq. (10.5.12) in section 10.4 (see (10.4.20)), all we have to do is to

substitute:

L 2 Yml (, ) = h 2 2 Yml (, ) = h 2 l (l + 1) Yml ( , )

with l = 0, 1, 2, K (10.5.14)

A further look to eq. (10.5.10) reveals another term, we came across in solving the Schrdingerequation for the rotators. It is L z = h and when applied to the -part of the sphericali

h

h

() = Nlm ( )

i

i

h

= Nlm ( )

m e im = hm Yml ( , )

2

L z Yml (, ) =

N lm ( )

e im

2

with

(10.5.15)

l m l

We have just seen that the magnitude of the total angular momentum L is quantized having

eigenvalues h l (l + 1) and that additionally L z is quantized by eigenvalues hm .

As long as we do not assign the problem to specific Cartesian direction - for instance by applying an

additional (magnetic) field- there is nothing specific about the z co-ordinate. The simple dependence

on occurs because we had chosen it to be perpendicular to z. We will later see, that this choice

makes the x and y component of the angular momentum non-measurable, as their contribution to the

probability density function vanishes (see eq. (10.4.25)). However, if we would have chosen x or

y to lie perpendicular to the angular momentum relative to them would turn out to be quantized,

and the remaining other would be non-determinable.

These results are really important, because we can now conclude, that any system with a spherically

symmetric potential U(r) -hence a central force problem, which can be separated from the angular

terms- has solutions for its angular terms as above.

Graphically we can summarise these considerations. As an example we consider l = 2 and hence

L = h l (l + 1) = h 6 . If a preferred direction exists (as in the presence of an external field) or

we simply chose it to be z, L z = hm with m = -2, -1, 0, 1, 2. Thus 5 different directions of the

angular momentum vector exist relative to the z-axis, as visualised in Fig. 10.12. Note that a

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

10 Rotational Motion

page: 77

completely parallel or anti-parallel alignment to the z-axis is not possible, since its maximum

projection on the preferred axis is lh , while having a length of h l (l + 1) > hl . (Only for very large

l ( l + 1) l , so that the object is able to rotate solely

around a preferred axis).

z

m = +2

2h

m = +1

h

h 6

0

h

m=0

m = -1

2h

m = -2

Possible alignments of L with respect to the z-axis.

As discussed above (and proven later) if we select z as a preferred axis, x- and y-component of the

angular momentum are uncertain or have equal probability to lie on cones (see Fig. 10.13) with halfapex-angles determined by = arccos m / l ( l + 1) . (Do not think of the angular momentum

vector sweeping out one of the cones, but simply lying at some position on the cones).

momentum vector

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

Excursus 2

Excursus 2:

page: 78

Operator:

2

2

2

=

+

x 2

y 2

The Laplacian is

(E2.1)

x = r cos

with r 2 = x 2 + y 2

(E2.2)

r = x2 + y2

or

y

sin

=

= tan

x

cos

and

y = r sin

and

or

= arctan

(E2.3)

y

x

(E2.4)

f

f

dr +

d

r

(E2.5)

f

f r

f

=

+

x

r x

x

(E2.6)

df =

hence

and

f

f r

f

=

+

y

r y

y

(E2.7)

12

1 2

r

2

1

=

x + y2

= 2x x 2 + y 2

=

x

x

2

x

2

x +y

x

= cos

r

y

y

1

y

y

sin

=

arctan

=

=

=

=

2

x

x

x

r

x2 1 + y

x2 + y 2

r2

2

(E2.8)

(E2.9)

r

=

y

y

= = sin

r

x2 + y2

1

=

y

x

1

1+

x2

x

x2 + y2

(E2.10)

cos

r

(E2.11)

Excursus 2

page: 79

Therefore, we can express the first partial derivatives of f by substituting (E2.8/9) into (E2.6) and

(E2.10/11) into (E2.7):

f

f

f sin

f

sin f

fx

=

cos

= cos

x

r

r

r

r

(E2.12)

f

f

cos f

f y

= sin

+

y

r

r

(E2.13)

2 f

x 2

2 f

y 2

f x

f x r

f x

=

+

r

r x

x

(E2.14)

f y

f y r

f y

=

+

y

r y

y

(E2.15)

We have to be careful, because f x and f y depend on r and ! Substituting (E2.12) and (E2.8/9)

into (E2.14):

2 f

x 2

f sin f

cos

r

r

f sin f

cos

cos

r

r

2 f

sin f

sin 2 f

= cos

+

r r

r 2

r 2

cos

f

2 f sin cos f

sin 2 f

sin + cos

r

r

r

r 2

= cos 2

2 f

r 2

sin

sin

+

+

+

r r

r

r

r

r

r2

r2

2

2 f

y 2

f

cos f

f

cos f cos

sin

+

sin +

sin

+

r

r

r

r

r r

= sin 2

2 f

r 2

+

+

+

+

r r

r

r

r

r

r2

r2

2

Excursus 2

page: 80

The Laplacian is then given by the sum of the last two equations:

2

2

2

2

2

2

2

2

2 f = f + f = sin 2 + cos 2 f + sin + cos f + sin + cos + f

r

r

x 2

y 2

r 2

r2

2

2

2

2 = +

x 2 y 2

r 2

1

1 2

+

r r r 2 2

1 2

1

r + 2 2

r r r

r

(E2.16)

where we used a nice abbreviation for the two terms that depend on r.

It can be shown (see [1] page 431- 433) that for orthogonal co-ordinates

(

(

)

)

h h

x

r

1

y = h h h hr h

r (h h )

z

r

( )

( )

( )

( )

(E2.17)

2

2

2

y

hr2 = x + + z

r

r

r

with

2

2

2

y

h2 = x + + z

y

h2 = x + + z

(E2.18)

2

and

2 = 2 + 2 + 2 =

2

2

2

x

1

hr h h

h h

hr h

h h

+ r

+

r hr r h h

(E2.19)

dx dy dz = J dr d d

( x, y, z )

=

( r , , )

x

r

y

r

z

r

(E2.20)

x

= hr h h

(E2.21)

Excursus 2

page: 81

For the 2D example in E2.1, we derive from eq. (E2.2):

( )

2

2

y

hr2 = x + = (cos )2 + (sin )2 = 1

r

r

2

y

h2 = x + = ( r sin )2 + (r cos )2 = r 2

2

1 r r

2 = 1 r + 1 1 = 1 r + 1

and hence: = and

r

r r r r r r r r r 2 2

The relation between Cartesian and polar co-ordinates is (see Fig. 10.6):

x = r sin cos

y = r sin sin

z = r cos

(E2.22)

= sin 2 (cos 2 + sin 2 ) + cos 2 = 1

hr2 = xr

( )

( )

2

2

2

y

h2 = x + + z = (r cos cos ) 2 + (r cos sin )2 + ( r sin )2 = r 2

y

h2 = x + + z = ( r sin sin )2 + (r sin cos )2 = r 2 sin 2

and hence (see (E2.17))

r 2 sin

sin r 2

r

r

1

1

= 2

(r sin ) = 2

r sin

r sin

r sin

(r )

r

(E2.23)

2

1

1

2 =

r

sin

+

(

sin

)

+

sin

r 2 sin r

=

1 2

1

1

r

+ 2

sin + 2

2 r

2

r

r sin 2

r

r sin

(E2.24)

dx dy dz = r 2 sin dr d d

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

(E2.24)

Excursion 2

page: 82

Tab. E2.1: You might find the following table generally useful:

co-ordinates:

Cartesian

x,y,z

hr

h

h

dV

2

x2

2D circular

x = r cos

3D-cylindrical

x = r cos

3D-spherical

x = r sin cos

y = r sin

y = r sin

y = r sin sin

z = z

1

h z = 1

r

z = r cos

1

r

rsinq

1

r

x

y

z

1 r r

r

r

r

1

r

z

sin r 2

r

1

r sin

r 2 sin

1 1 2

r +

r r r r 2 2

1 1 2

2

+

r +

r r r r 2 2 z 2

1 2

1

1

2

r

+

sin +

r 2 sin 2 2

r 2 r r

r 2 sin

r dr d dz

r 2 sin dr d d

2

2

+ 2+ 2

dx dy dz

r dr d

page: 83

Detail (Solution of differential eq.)

MAPLE exercise

To know:

1. Coulomb potential, effective potential, angular momentum barrier, energy

spectrum, Schrdinger-equation for central force problem.

2. Bohr-model, -radius

3. Radial waveform (Laguerre polynomials)*

4. Solutions*

(r , , ) = N nlmR (r ) () ()

En =

Z 2 e 4

802h 2 n 2

5.

6.

7.

8.

l n 1 and

l m l

Radial distribution function (construction, spherical Jacobian)

Orbitals*

Basic idea of hybrid orbitals

* not in detail, but their dependence (the most simple you could remember!)

11 Hydrogenic Atom

page: 84

11.1 Motion in a Coulomb field

The motion of a single electron in the Coulomb-field of charged nucleus is to be solved. We

remember that the force varies as F(r) 1/r2 and hence the potential energy (F = -dU/dr) as

U(r) 1/r. To be exact the Coulomb-potential between a nucleus of charge Ze and an electron of

charge -e is:

U (r ) =

Ze 2

40 r

(11.1.1)

with 0 = 8.854188 10 12 C 2 / (Jm ) the permittivity in the vacuum. As introduced in part 10.1

we can simplify the two-particle problem to a quasi one-particle problem using its reduced mass

m m

= e nucleus , where mnucleus is the mass of the nucleus.

me + mnucleus

me mp

me + mp

h2 2

Ze 2

= E

2

40 r

(11.1.2)

Because the problem is similar to the rotation of a particle on the surface on the sphere, but now with

a radial potential, an expression of this equation in spherical co-ordinates, (r , , ) , appears to be

appropriate (using eqn. (E2.24)) :

1 2

1

1

2

2 r

+ 2

sin + 2 2

( r , , ) +

r sin

r sin 2

r r r

2

Ze 2

E +

( r , , )

4 0 r

h 2

(11.1.3)

=

(r , , ) = R( r ) ( ) ( )

(11.1.4)

11 Hydrogenic Atom

page: 85

d 2 dR

R d

d

R d 2

r

+

sin

+

+

d

r 2 dr dr

r 2 sin d

r 2 sin 2 d 2

(11.1.5)

2

Ze 2

E

+

R

40 r

h 2

r2

following the typical separation-procedure eq. (11.1.5) is multiplied by

:

R

1 d 2 dR

1

d

d

1

d 2

2

Ze 2 2

r

+

sin

+

+

E

+

r =

R dr dr

sin d

d

40 r

sin 2 d 2

h 2

0 (11.1.6)

and rearranged:

1

1 d 2 dR

2

Ze 2 2

d

d

1

d2

r

+

E

+

r

=

sin

(11.1.7)

2

2

R dr dr

40 r

sin

h 2

sin

Hence, the problem is separated into a radial part (left) and an angular part (right). The right side

(square brackets) we identify as the differential equation for the particle on a sphere (see eq.

(10.4.15) to (10.4.20)) and can readily insert the solutions (spherical harmonics):

1 d 2 dR

2

Ze 2 2 (10 .4 .15 )

1 2

=

r

+ 2 E +

r

R dr dr

40 r

h

(10 . 4. 19 )

Yml

2 Yml

(10 .4 .20 )

1 d 2 dR

2

Ze 2 2

r

+ 2 E +

r l ( l + 1) = 0

R dr dr

40 r

h

1 2 d2 R

dR

2

Ze 2 2

+ 2r +

r

E +

r l ( l + 1) = 0

R dr 2

dr

40 r

h 2

d 2 R( r )

dr 2

(11.1.8)

l (l + 1)

R

r2

(11.1.9)

2

2 dR( r )

Ze 2

l (l + 1)

+

+ 2 E+

R( r ) = 0

r dr

4 0 r

h

r 2

This is not surprising, because the problem can be understood as a particle moving on a collection of

spherical shells. However, what is left to find is its distribution over these shells, the radial part.

11 Hydrogenic Atom

page: 86

Now we want to go -in a way- some steps backwards, to understand our findings. Therefore, we

express equation (11.1.9) in the standard form of the Schrdinger-equation:

h 2 l ( l + 1)

h2 1 d 2 d

r

R

(

r

)

+

+

U

(

r

)

R( r )

2

2 r 2 dr dr

2r

= ER( r )

h 2

R( r ) + U eff ( r ) R (r ) = ER( r )

2

(11.1.10)

h 2 l (l + 1)

U e ff [10-18J]

U [10 -17J]

2r 2

Coulomb-potential from eq. (11.1.1). The first term appears due to the rotation of the electron,

which counter-acts the Coulomb-potential as a repulsive core for l > 0. It becomes infinitely high as

r 0, hence prevents the system to collapse, and is therefore called angular momentum

barrier. The nature of the two potentials and their sum is depicted in Fig. 11.1.

1.0

0.8

a)

0.6

b)

l=3

1

0.4

0.2

a.m.b.

r []

-0.2

10

U eff( r)

U( r)

r []

4

10

-1

-0.8

-1.0

l=1

-0.4

-0.6

l=2

l=0

-2

Fig. 11.1: Potentials for 1H: a) green: Coulomb-potential, U(r); blue: angular momentum barrier

(a.m.b.) and red curve: sum of a) and b), the effective potential Ueff(r). Calculations for

l = 1. b) Ueff(r) for l = 0, 1, 2 and 3.

In Fig. 11.1 we recognise the attracting nature of the Coulomb-potential (negative) and the repelling

character of the angular momentum barrier. If the energy becomes higher then the Coulomb-term

and the angular momentum term dominates, the particle is retracted from the nucleus and must

behave like a free (unbound) particle, hence without quantized energy states (energies form a

continuum, see Fig. 11.2). This process is called ionisation and defined by Ueff. Due to the wider

potential range for higher energies, we can also conclude that the energy levels for the bound states

must converge to that limit. Due to the finite value of the potential at a discrete bound energy state we

can finally expect the particle to tunnel beyond the classical limits (that is where the energy level

meets the potential).

11 Hydrogenic Atom

U eff [10-18J]

page: 87

continuum of unbound,

free-particle states

r []

discrete,

bound

states

10

-1

to be expected from general considerations.

The aim of this part is to solve eq. (11.1.9). This will be done in elementary steps, which requires

many substitutions to guide through the essential maths. We start with the last line of (11.1.9) and

rewrite it in a shorter notation:

d 2 R( r )

dr 2

2

2 dR( r )

Ze 2

l (l + 1)

+ 2 E +

R( r ) = 0

r dr

40 r

h

r 2

2

2

Ze 2

l (l + 1)

R + R + 2 E +

R = 0

r

4 0 r

h

r 2

(11.2.1)

E

h2

and

Ze 2

40 h 2

(11.2.2)

leading to:

R +

2

2

l (l + 1)

R + 2R +

R

R =0

r

r

r2

(11.2.3)

We are now testing the equation for r , meaning the electron leaves the nucleus to become a free

particle. In eq, (11.2.3) that causes the terms that depend on 1/r to vanish:

+ 2R = 0

R

(11.2.4)

11 Hydrogenic Atom

page: 88

R ( r ) = A exp i 2 r + B exp + i 2 r

(11.2.5)

where E represents the energy. This general (complex) solution can only be normalised (to

the real value 1), when we assume E or < 0, so that i 2 = i 1 2 = 2 with a

positive radicand. (Try these normalisations as examples or alternatively substitute with a negative,

see eq. (11.2.8)) This can also be suggested when looking at Fig. 11.2 (but now we have

mathematical proof)! The normalisation condition then reads as:

(A exp (

2 r + B exp 2 r

))2 dr = 1

(11.2.6)

The first term becomes infinite for r and is hence unacceptable, because we know that the

wavefunction must vanish, while the second (becoming zero) is acceptable for these conditions.

Therefore, A = 0 and

R ( r ) = B exp 2 r

(11.2.7)

2 =

2E

h

(11.2.8)

Now, we try a first approach for a general solution by incorporating the knowledge for r and

ignore B, knowing that the final normalisation of the wavefunction must recover it.

R( r ) = R f ( r ) = e r f ( r )

(11.2.9)

R (r ) = e r f ( r )

R( r ) = e r f ( r ) e r f ( r ) = e r ( f ( r ) f ( r ) )

R( r ) = e r ( f (r ) f (r ) ) e r ( f (r ) f ( r ) )

= e r f ( r ) 2f ( r ) + 2 f (r )

(11.2.10)

These results are used in the radial part of the Schrdinger-equation (eq. (11.2.3)):

e r f ( r ) 2 f (r ) + 2 f ( r ) +

2 r

2 l (l + 1) r

e ( f ( r ) f ( r ) ) + 2 +

f (r ) = 0

e

r

r

r2

11 Hydrogenic Atom

2

2

2 l ( l + 1)

f ( r )

f (r ) + 2 +

2 f (r) = 0

r

r

r

2( + ) l (l + 1)

1

f ( r ) + 2 f ( r ) + 2 + 2 +

f (r) = 0

r

r

r2

page: 89

f ( r ) 2 f (r ) + 2 f (r ) +

(11.2.11)

2( + ) l ( l + 1)

1

f ( r ) + 2 f (r ) +

f (r) = 0

r

r

r2

(11.2.12)

So far things do not really look simplified. We try another approach for the evaluation of the

unknown part of this equation f(r) by expressing is as a power series (with coefficients b) and trying

to find an upper limit (quantum number) to meet the boundary conditions, which means that the series

is transformed into a polynomial of a degree given by this upper limit:

f (r )

bq r q

and hence R( r ) = e r

bq r q

(11.2.13)

q =0

q= 0

for substitution into eq. (11.2.12), we calculate the first and second derivative:

f (r ) =

bq r q

q

f ( r ) =

q bqr q 1

(11.2.14)

f ( r ) =

q(q 1) bq r q 2

q

q

[q (q 1) + 2q l (l + 1)]bq r

q 2

[(2 2 ) 2q ]bq r

q 1

=0

=0

(11.2.15)

In order to become zero the coefficients for each power of r have to cancel. Hence, we match the

indices for r q and set them to be zero:

[( q + 2)( q + 1)

bq + 2

bq + 1

+ 2(q + 2) l ( l + 1) ]bq + 2 2 [( q + 1) ( )] bq +1 = 0

2 [( q + 1) ( ) ]

2( q + 2 )

=

[(q + 2)( q + 1) + 2( q + 2) l (l + 1) ] ( q + 2)( q + 3) l (l + 1)

(11.2.16)

11 Hydrogenic Atom

page: 90

We further simplify this by reducing the index, q, by 1, which results in the following recursionformula:

bq +1 = bq

2((q 1) + 2 )

( q + 1)

= 2bq

( q + 2)( q + 1) l (l + 1)

(q + 2)( q + 1) l (l + 1)

(11.2.17)

The next step is to find a limiting case for q and hence dominating and l2, hence assuming q >

l:

2bq

(q + 1)

lim bq +1 2bq

=

(q + 2)( q + 1)

q

q+2

(11.2.18)

The purpose of a recursion-formula is to address the next higher coefficient by a lower. So we want

to try to express bq by b0 (the lowest coefficient relating to a constant). We start by calculating b1, b2

etc... to end up with a general expression for large q:

2

1

b1 b0 = (2 )b0

3

3

1

1

b2 (2)b1 =

(2)2 b0

4

3 4

1

1

b3 (2)b2 =

(2)3 b0

5

3 4 5

...

2

bq = (2)q b0

q!

(11.2.19)

ar

q =0

hence R( r )

( 4 .2 .13 )

(ar )q

q!

e r

bq r q

( 4 .2 .19 )

q =0

e r 2b0

q =0

(2r )q

q!

(11.2.20)

R( r ) = 2b0 e r e 2 r = 2b0 e r

Without loss of generality, we can deposit the 2 in the normalisation constant and get

R (r ) = b0 e r

(11.2.21)

However, this cannot be the final result, because we have to remember the boundary condition

lim R( r ) = 0 and from the definition in (11.2.8) we reassure that > 0 ! Therefore an upper

r

limit p has to be introduced to stop the series and convert it into a polynomial of degree p, e.g.

11 Hydrogenic Atom

page: 91

0 q p., which means that the series stops after p or b p +1 = 0 . Hence b p + 2 = 0 and all

following coefficients vanish due to eq. (11.2.17) and for b p 0 this gives:

b p +1 = 2b p

( p + 1)

= 0

( p + 2)( p + 1) l (l + 1)

(11.2.22)

The equation is fulfilled for a) the nominator = 0 and b) the denominator 0, or:

( p + 1) =

p +1 n

a)

(11.2.23)

(1

p4

+422

)( 4

p +4

1) l1

(l2

+3

1) 0

3

b)

>0

>0

( p + 2)( p + 1) >

n( n + 1) >

n >

n

l (l + 1)

l (l + 1)

l

l +1

(11.2.24)

As at the start of the derivation of this formula we (c.f. eq. (11.2.18)) we have to assume p+1 < l.

As expected, we found another quantum number n, related to l, which is related to m (cf. eq.

(10.4.23)). From condition a) we can directly calculate the energies associated with the radial part of

the wavefunction, by re-substituting (11.2.2) and (11.2.8):

2E

Ze 2

=

h

40 h 2 n

En =

Z 2 e 4

32 2 20 h 2 n 2

(11.2.25)

Z 2 e 4

8 20 h 2 n 2

for n l + 1 = 1, 2, 3,K

This is exactly the result Bohr found in his treatment of the hydrogen atom and we also identify our

parameter

=

1

rB

(11.2.26)

11 Hydrogenic Atom

page: 92

The only thing left to do, is the exact determination of the wavefunction R(r). We summarise our

equipment for this task:

r n 1 q

Rn , l ( r ) = exp

bq r

nrB q = 0

1

1

, =

,

rB

nrB

for n l + 1 = 1, 2, 3,K

(q + 1)

coefficien ts : bq +1 = 2bq

( q + 2)( q + 1) l (l + 1)

bq +1 (q + 2)( q + 1) l (l + 1)

bq =

2

( q + 1)

and start with the lowest allowed state: n = 1, hence l = 0

r

R1,0 ( r ) = b0 exp

rB

R1,0 () = b0 e

(11.2.27)

r

with =

rB

Normalisation gives

R12, 0 ( ) d

=0

= b02

=0

b02

d =

=1

2

(11.2.28)

R1,0 () =

2 e

(11.2.29)

Now the steps are repeated for n = 2, hence we have to distinguish l = 0, 1 or R2, 0 ( r ) and

R2,1 ( r ) . Generally this is determined by:

r

R2 ,l ( r ) = exp

nrB

1

r

bq r q = exp

q =0

nrB

a) case: n = 2, l = 0

b1 = 2b0

r

hence, R2, 0 ( ) = exp

2rB

b

b0 0

2rB

1

2 rB

b

= 0

2 1 0

2 rB

rB

= N 2 ,0 1 e 2

2

(11.2.31)

11 Hydrogenic Atom

page: 93

b) case: n = 2, l = 1

If we would proceed as in the previous case eq. (11.2.17) yields zero in the denominator.

Therefore, we use the formula backwards

bq +1 (q + 2)( q + 1) l (l + 1)

bq =

2

( q + 1)

therefore we determine b0. and use b1 for normalisation:

b

2 2

b0 = 1

= 0

1

2

1

2 rB

hence R2,1 () =

b1 rB e

= N2 ,1 e

rB

(11.2.32)

Note, that the final results in a) and b) contain the associated normalisation constants N 2 , 0 and

N 2 ,1 .

Continuation of this procedure gives the following table of the radial-parts of the wavefunction for the

hydrogen-like atom, which are depicted in Fig. 11.3. (Note: That Fig. 11.3 shows the radial part

of the wavefunction and not a 3D-projection of the real distribution of the electron, since the angular

terms have been neglected so far)

Table 11.1: The radial-parts Rn, l () of the wavefunction for the hydrogen-like atom as the function

of the radius in multiples of the Bohr-radius.

n

Rn, l ()

R1,0 =

2 e

1

R2, 0 =

(2 ) e 2

2

1

R2,1 =

e 2

2

2

R3, 0 =

27 18 + 22 e 3

27

R3,1 =

2

9 3

(6 ) e

2

2 2 3

R3, 2 =

e

27

11 Hydrogenic Atom

page: 94

Fig. 11.3: Left: The radial part of the wavefunction Rnl() for n=1,2 and 3. Right: The

corresponding probability density function Pnl().

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

11 Hydrogenic Atom

page: 95

The radial part of the eigen-functions of the hydrogenic atom are another ortho-normal class of

polynomials (like the Hermite and Legendre polynomials), called associated Laguerre polynomials:

They are solutions of the so-called associated Laguerre equation, in which eq. (11.2.1) can be

transformed.

xf ( x) + (k + 1 x ) f ( x) + j f ( x ) = 0

solutions : f ( x) = L kj ( x)

associated Laguerre polynomial s :

L jk ( x ) = (1) k

(11.2.33)

j+ k

j + k xi

(1) i

dx k i = 0

i i!

dk

Rnl () = N nl e

/ n

2l + 1

Ln l 1 ()

n

(11.2.34)

2 ( n l 1)!

n 2n(n + l )!

N nl =

The complete solution for an electron in a Coulomb-potential (hydrogenic atom) was calculated by

separation of variables, where the radial part was solved in the previous part, after we have

recognised that the angular parts were already solved in chapter 10 with the spherical harmonics,

Hence, the eigen-functions of the hydrogenic atom are given according to eq. (11.1.4):

Hydrogenic Atom:

(r , , ) = N nlm R( r ) ( ) ( )

l

n

and =

r

rB

N nlm =

En =

Ze 2

40 h 2

3

2 ( n l 1)! (2l + 1)( l m )!

n 2n(n + l )! 4 ( l + m )!

Z 2 e 4

8 20 h 2 n 2

with n = 1, 2, 3,... and

l n 1 and

l m l

(11.3.1)

11 Hydrogenic Atom

page: 96

As expected the three degrees of freedom in motion generate three quantisation conditions,

described by the three quantum numbers n, m and l. Different nomenclature is in use for them:

n

because n defines the shell

n = 1, 2, 3, 4,....

n = K, L, M, N, ....

l = 0, 1, 2, 3, 4, 5..., (n-1)

l = s, p, d, f, g, h

spectroscopic notation:

m

l m l

m = -l, (-l+1), ..., , , , , , , ,... , (l-1), l

spectroscopic notation:

The following table is illustrating the mutual dependence of the quantum numbers.

Tab. 11.2: Summary of the interdependence of the quantum numbers for the hydrogenic atom, for

n = 1, 2 and 3 including nomenclature and degeneracy. (Neglecting the spin of the

electron, which is done in the next lecture)

n

1

2

3

l

m

0

0

0

0

name

sp.n.*

1s

2s

1s

2s

-1

1

0

2p

2p

2p

0

0

-1

3s

2p

D(n)**

1

4

*spectroscopic name including m-notation.

** D(n) degeneracy of state.

3s

1

0

-2

-1

3p

3p

3p

2

0

3d

3d

3d

3p

3d

3d

3d

The energy is determined by n only (cf. eq. (11.2.25)). Hence we have 2l+1 degenerate states

(span of m), where the span of l is defined by n-1. Therefore the degeneracy of a state n is given by:

n 1

D( n) =

n

(11.3.2)

l =0

Combining the equations in (11.3.1) gives the complete wavefunctions for the hydrogenic atom as

listed in Tab. 11.3:

11 Hydrogenic Atom

page: 97

Tab. 11.3: The complete wavefunctions, nlm ( , , ) , of the hydrogenic atom for

n = 1, 2 and 3.

Name

nlm ( , , )

1s

1

e

2s

1

(2 )e / 2

4 2

2p

-1

1

8

2p

2p

e / 2 sin e i

1

e / 2 cos

4 2

1

8

e / 2 sin e i

3s

1

27 18 + 2 2 e / 3

81 3

3p

-1

1

(6 ) e / 3 sin e i

81

3p

2

(6 ) e / 3 cos

81

3p

1

(6 ) e / 3 sin ei

81

3d

-2

1

2 e / 3 sin 2 e 2i

162

3d

-1

1

2 e / 3 sin cos e i

81

3d

1

81 6

2 e / 3 3 cos 2 1

3d

1

2 e / 3 sin cos ei

81

3d

1

2 e / 3 sin 2 e 2i

162

11 Hydrogenic Atom

page: 98

For the calculation of the normalisation constant N nlm it is important to realise, that the integration is

(preferably) done in spherical co-ordinates (cf. Tab. E2.1) and the integrand can be further

simplified according to eq. (10.4.25), where we have learned that the -term behaves constant.

2

N nlm

2

N nlm

*( x, y, z)(x, y, z)dxdydz

( E 2. 1)

0 0 0

2

* ( r , , ) ( r , , ) r 2 sin dr dd

(10 . 4. 25 )

(11.3.3)

r = 0 =0 =0

2

N nlm

2

[rR(r )()]

sin drd = 1

r =0 =0

This procedure can be easily understood, when we have a look at the s-orbitals, which according to

l = 0 have spherical symmetry. Hence, we can replace the radial probability distribution function (e.g.

in Fig. 11.3/right) by an integration over spherical shells of thickness dr. Hence, we have to substitute

the probing volume (d) of the radial probability distribution function, Pn 0 () d = Rn20 () d ,

with the volume of the spherical shells (42 d) to get the projection of the three-dimensional

~

distribution function, Pn0 () (we call it the radial distribution function), of the electron on the

radius or

~

Pn 0 () d = 42 Rn20 () d

(11.3.4)

This principle is illustrated in Fig. 11.4 using the 1s-orbital as an example. From the plot of the

radial distribution function for the 1s, 2s and 3s-orbital (see Fig. 11.5) the Bohrs idea of shells, in

which the electron is located can be anticipated, but we also realise, that the nth shell has only the

maximum probability. The electron has a finite probability to be found in lower shells. (Closer

examination also uncovers that -except of 1s- that the maximum is not at integer multiples of rB) We

also realise that there is a small but non-zero probability to find the electron inside the nucleus,

assuming the nucleus has a finite radius. This is of great importance for nuclear reaction e.g. +decay via electron capture.

Finally we want to visualise the atomic orbitals, which is a difficult task, because we have a 3Dwavefunction which has a different values at the co-ordinates ,, . Therefore, we have to depict it

either as a cloud of varying density, or we have to pick a certain threshold of probability to which we

assign a surface (isosurface). Both ways of visualisation are shown in Tab. 11.4, where the different

signs of the lobes have been colour-coded (positive = red, negative = green).

For an on-line visualisation, you can download Orbital-Viewer (a program from D. Manthey) from

the webpage (http://wwwnmr.ukc.ac.uk/staff/pb/teach/PH502/Aos/ ao.html) of the

course.

11 Hydrogenic Atom

page: 99

P()

~

P ()

d

1

r=rB

Fig. 11.4: Illustration for the construction of the radial probability density function for the 1s-orbital:

Upper: If an infinitesimal small and constant sampling volume d is scanned along the

radius, we will receive the radial-part of the electron density P(). (If additionally the

detector would be moved on a circle, for each the same value would be recorded. The

1s-orbital is isotropic.) Lower: Now the electron density is measured over a spherical

~

shell of thickness d, to determine the radial probability distribution function P () , which

has a maximum at the Bohr radius ( = 1).

16

14

2.5

~

P10( )

2

1.5

1

2

0.5

0

12

10

8

~

P20( )

10

15

20

25

30

10

15

20

25

30

P~30 ()

6

4

2

0

10

15

20

25

30

Fig. 11.5: The radial distribution function (not-normalised) for the first three s-states (l = 0).

Compare with the according states in Fig. 11.3.

11 Hydrogenic Atom

page: 100

Tab. 11.4: Atomic orbitals for hydrogenic atoms for n = 1, 2 and 3. On the left of each cell the orbital is shown as a probability plot using 10000 points. On

the right (for ns-orbitals in the centre) an isosurface (corresponding to a probability of 10-4) is shown. For the ns-orbitals additionally, an octant of

this isosurface has been cut away to show the inner shells. Red colour corresponds to positive lobes, green to negative.

0/s

0/s

-2

-1

1/p

0/s

1/p

2/d

m

0

+1

+2

11 Hydrogenic Atom

page: 101

Fig. 11.6: Energy levels for hydrogen 1H including the l 5. Energy is measured in units of

h 2 /( 2rB2 ) .

We have seen from Tab. 11.3 that the wavefunctions of the hydrogenic atom are partially real and

partially imaginary. The first case applies for m = 0 the latter for m 0. The there are n2 degenerated

eigen-functions belonging to the same n, we can create new functions by linear combination, which

are entirely real. This has practical applications in chemistry. Since the new functions are created

from the set of solutions, we call them hybrid orbitals. For instance

1

(2 p + 2 p ) = 1 e / 2 sin [cos + i sin ] + e / 2 sin [cos i sin ]

8 2

(E2.22)

x

2

1

/ 2

[

]

=

e

sin cos

=

e / 2 2px

8 2

4 2

rB

Analogously we get:

(E2.22)

y

1

1

(2 p 2 p ) = 1 e / 2 sin sin =

e / 2 2p y

4 2

4 2

rB

2 p =

(E2. 22 )

z

1 2 / 2

1

e

cos =

e / 2 2p z

8

4 2

rB

Hence, we receive three equivalent 2p-functions, which can be correlated to the three Cartesian coordinates. This is useful for geometrical considerations (e.g. chemical complexes).

Similarly we proceed with the other wavefunctions (see Tab. 11.5)

Dr. P. Blmler, School of Physical Sciences, University of Canterbury, UK

11 Hydrogenic Atom

page: 102

Symbol

combination

hybrid wavefunction

1s

1s

1

e

2s

2s

1

(2 )e / 2

4 2

2pz

2p

1

e / 2 cos

4 2

2px

1

(2p + 2p )

2

1

e / 2 sin cos

4 2

2py

m1

1

(2p 2p )

2

1

e / 2 sin sin

4 2

3s

3s

1

27 18 + 2 2 e / 3

81 3

3pz

3p

2

(6 ) e / 3 cos

81

3px

1

(3p + 3p )

2

2

(6 ) e / 3 sin cos

81

3py

m1

1

(3p 3p)

2

2

(6 ) e / 3 sin sin

81

3d z 2

3d

3dxz

1

(3d + 3d )

2

2 2 / 3

e

sin cos cos

81

3dyz

m1

i

(3d 3d )

2

2 2 / 3

e

sin cos sin

81

3d x 2 y 2 3

1

(3d + 3d )

2

3dxy

1

81 6

m2

i

(3d 3d )

2

1

81 2

1

81 2

2 e / 3 3 cos 2 1

2 e / 3 sin 2 cos 2

2 e / 3 sin 2 sin 2

The hybrid orbitals do not look different from those in Tab. 11.4. They are just transferred back to

Cartesian co-ordinates (with slightly different normalisation constants).

Thanks!

page: 103

Acknowledgements:

I would like to thank Dr. C. Isenberg to provide access to his notes for a first layout of the course.

They have turned out to be very helpful and guiding for a new lecturer. I also want to thank Mr. Ian

Campbell for proof-reading the first draft of the manuscript.

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