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Pilani Campus

CHEM F111 : General Chemistry

Lecture 3

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Summary (Lecture 2)
Foundation of Quantum Mechanics
Why Quantum Mechanics ?
Wavefunction
Characteristics of an acceptable wavefunction
Single-valued

Continuous & differential

Bounded
Normalized
Observables & Operators
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Probability Density is more Informative

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Use of Eigen value Function

For determining the value of an observable (property, e.g. p, E)
for a physical system:
-Operate the operator (p, E) on well-behaved wavefunction ()
of that system.
-This operator-function combination should form eigen value
equation and the corresponding eigen value = value of that
observable.
Information about the system could only be known if we know the
eigen value of observable.

A given wavefunction is an eigen function of some operators by not

an eigen function of others.

Not all observables are determined by any one wavefunction.

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Energy: Hamiltonian Operator

= mv2/2 + V = p2/2m + V

E (total Energy) = KE + PE

Energy Operator : Hamiltonian ( H ) operator

px=

p2
2 d 2
H
..In 1-D
V
V ( x)
2
2m
2m dx
2 2
2
2
2 2 2 V ( x, y, z ) ..In 3-D

Cartesian
2m x y
z
coordinates

2 V
2m

Laplacian operator

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Time-independent Schrdinger Eq.

Energy of a system could be known by operating total energy
operator on the wavefunction.
The wavefunction (for stationary states; independent of time)
satisfies the Schrdinger equation:

= E

2 2

2
2
2 2 2 V ( x, y, z ) ( x, y, z ) E ( x, y, z )

y
z
2m x

When is operated upon by , returns the multiplied by E; a

category of equation called eigen (=own) value eqn.
Second order differential equation: the solutions will provide the
energies of possible states
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Next What ?

? How to extract information from the solutions

? How to solve schrdinger equation for the system

? How to define wavefunction of any system ?

General form of Schrdinger Equation
Observables & Operators
Acceptable wavefunction
Need for Quantum Mechanics

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Application to a Microscopic system

Translation Motion in 1-Dimension: Particle in a Box
Consider a particle of mass m travelling along x-axis,
confined to a length L by infinite potential barriers at x = 0
and x = L (infinitely deep potential well)
V=0

For x < 0 and x > L,

= 0 since
probability of finding
the particle in these
V = regions is zero.

V=

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Particle in one-dimension box

Bead free to slide
between two stops

QM: wave associated

with particle
= sin kx or cos kx or
a combination of both

Boundary conditions must be

satisfied by the wavefunctions

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Particle in 1-D box: Wavefunction

Let the trial wavefunction be ( x) A sin kx B coskx
Applying the boundary condition at x = 0 and L gives

(0) 0

B cos k 0 0 B 0

( L) 0

A sin kL B cos kL 0

So, we obtain: A sin kL 0

Now A 0; otherwise will be 0 everywhere.
Hence,
sin kL 0, kL n
n 1,2,3,
n cannot be 0
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Particle in 1-D box: Normalized wavefunction

The wave function for the system will be

n
( x) A sin
x
n 1,2,3,
L
Now, if (x) is normalized wave function then

nx
nx
0 * ( x) ( x)dx ( A sin L ) * ( A sin L )dx 1
0
L

nx
A sin
dx 1
L
0
L

Solution gives A2L/2 =1

or A = (2/L)1/2

2 n
Normalized wave function for particle ( x)
sin
L L
in a 1-D Box
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Particle in 1-D box: Calculating Energy

( x)

2 n
sin
L L

=E

2 d 2
2 d 2 2
n

(
x
)

sin

2
2m dx 2
2m dx L L

2 n

2mL

2 d n
cos
x

L dx L
h2n2 2
h2n2
n

sin
x

[ ( x)]
2
2
8mL L L
8mL

n2h2
En
8mL2

n = 1, 2,

Quantized energies of the paricle in a 1-D box; n: quantum number

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Ground State wavefunction and Energy

2 1
1
sin
L L

12 h 2
En 1
2
8mL
2

n h
p
En

2
8mL
2m
h nh
p
2L
2L

If n = 0; then = 0 everywhere and particle

vanishes (Not possible).
The energy at lowest cannot be zero;
consequence of uncertainty principle: particle
is within the box, so uncertainty in position,
x cannot be infinite; px (or energy) cannot
be zero.

Ground state energy: h2/8mL2 :Zero point energy

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Plot of wavefunctions vs position

= 2L/n; where n = 1,2,3,4

= 2L/3
3

2 3
sin
L L

= L/2

2 1
sin
L L

=L

= 2L
1

2 4
sin
L L

2 2
sin
L L

The wavefunctions are all symmetric or antisymmetric about the

midpoint of the box
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Probability Amplitude (b) & Density (c)

32 h 2
E3
9 E1
2
8mL

node

22 h 2
E2
4 E1
2
8mL

12 h 2
E1
8mL2
n 1 nodes in n, energy increases with increasing
number of nodes, no nodes in ground state
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Classical Limit
n2h2
En
8mL2

(i) E depend on L, the size of the system and m,

the mass of the particle.
(ii) Greater the value of L or m, the less important
are the effects of quantization on translational
motion: classical limit

(iii) As n becomes very large, the probability

distribution becomes uniform (continuous)
over the entire length of the box.
At sufficiently high energies, the quantum
mechanics agrees with classical mechanics.
Correspondence principle
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Particle in two dimensional (2-D) box

A two-dimensional square
well.
Potential energy is zero
between x = 0 and x = L1 and
y= 0 and y = L2,
Rises sharply to infinity at the
walls.

( x, y ) X ( x).Y ( y )
x X(x) = Ex X(x)
y Y(y) = Ey Y(y)

E= Ex + Ey
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Particle in 2-D box: Schrdinger Equation

2 d 2
d2
2 2 ( x, y ) ( E x E y ) ( x, y )

2m dx
dy
2 d 2
d2
2 2 X ( x)Y ( y ) ( E x E y ) X ( x)Y ( y )

2m dx
dy

On Solving

nx,ny ( x, y) X nx ( x).Yny ( y)
2

nx x
2

X x
sin
L1
L1

..

ny x
2

Y y
sin
L2
L2

..

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nx h 2
Ex
2
8mL1
2 2
ny h
Ey
2
8mL2
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Particle in 2-D box: Wavefunction & Energy

nxx n yy
2 2
sin

( x, y)
sin
L1 L2 L1 L2
2

ny h2

nx h
E

Where nx= 1,2,3.; ny=1,2,3

2
2
8mL1 8mL2
Now, when L1 = L2

(nx n y )h 2
2

8mL2

nx= 1 & ny=1 : Ground state energy of particle in 2-D box (square)
nx= 1, ny=2 & nx= 2, ny=1 : Degenerate Energy level
(Double degenerate states)
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Particle in 2-D box (square): Wavefunctions

2 , 2 ( x, y )

2 2x 2y
sin
sin

L L L

E2, 2

Non Degenerate state

1, 2 ( x, y )

2 x 2y
sin sin

L L L

2,1 ( x, y )

2 2x y
sin
sin
L L L

E2, 1

E1, 2

Doubly Degenerate states

2-fold degenerate

1,1 ( x, y )

2 x y
sin sin
L L L

E2 , 2

8h 2

8mL2

E1, 2

5h 2
E2,1
8mL2

2h 2
E1,1
2
8
mL
Non Degenerate state
E1, 1

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