Erpc Chapter13

Physical Chemistry 2
nd
Edition
Thomas Engel, Philip Reid
Chapter 13
The Schrdinger Equation
2010 Pearson Education South Asia Pte Ltd
nd
Edition
Chapter 13: The Schrdinger Equation
Objectives
Key concepts of operators, eigenfunctions,
wave functions, and eigenvalues.
nd
Edition
Outline
1. What Determines If a System Needs to Be
Described Using Quantum Mechanics?
2. Classical Waves and the Nondispersive Wave
Equation
3. Waves Are Conveniently Represented as
Complex Functions
4. Quantum Mechanical Waves and the
Schrdinger Equation
nd
Edition
Outline
1. Solving the Schrdinger Equation: Operators,
Observables, Eigenfunctions, and
Eigenvalues
2. The Eigenfunctions of a Quantum Mechanical
Operator Are Orthogonal
3. The Eigenfunctions of a Quantum Mechanical
Operator Form a Complete Set
4. Summing Up the New Concepts
nd
Edition
13.1 What Determines If a System Needs to Be Described Using
Quantum Mechanics?
Particles and waves in quantum mechanics are
not separate and distinct entities.
Waves can show particle-like properties and
particles can also show wave-like properties.
nd
Edition
13.1 What Determines If a System Needs to Be Described Using
Quantum Mechanics?
In a quantum mechanical system, only certain
values of the energy are allowed, and such
system has a discrete energy spectrum.
Thus, Boltzmann distribution is used.

where n = number of atoms
= energy
| | kT e e
j
i
j
i j i
e
g
g
n
n
/
=
nd
Edition
Example 13.1
Consider a system of 1000 particles that can only have
two energies, , with . The difference
in the energy between these two values is .
Assume that g
1
=g
2
=1.

a. Graph the number of particles, n
1
and n
2
, in states
as a function of . Explain your
result.
b. At what value of do 750 of the particles have
the energy ?
2 1
and c c
1 2
c c c = A
2 1
c c >
2 1
and c c
c A / kT
c A / kT
1
c
nd
Edition
Solution
We can write down the following two equations:

Solve these two equations for n
2
and n
1
to obtain
1000 and /
2 1
/
1 2
= + =
A
n n e n n
kT c
kT
kT
kT
e
n
e
e
n
/
1
/
/
2
1
1000
1
1000
c
c
c
A
A
A
+
=
+
=
nd
Edition
Solution
Part (b) is solved graphically. The parameter n
1
is
shown as a function of on an expanded
scale on the right side of the preceding graphs,
which shows that n
1
=750 for .
91 . 0 / = Ac kT
c A / kT
nd
Edition
13.2 Classical Waves and the Nondispersive Wave Equation
13.1 Transverse, Longitudinal, and Surface Waves

A wave can be represented pictorially by
a succession of wave fronts, where the
amplitude has a maximum or minimum value.

nd
Edition
13.2 Classical Waves and the Nondispersive Wave
Equation
The wave amplitude is:

It is convenient to combine
constants and variables to
write the wave amplitude as

where k = 2 (wave vector)
= 2v (angular frequency)
( )
|
.
|
\
|
= +
T
t x
A t x
t 2 sin ,
( ) ( ) wt kx A t x = + sin ,
nd
Edition
13.2 Classical Waves and the Nondispersive Wave
Equation
13.2 Interference of Two Traveling Waves

For wave propagation in a medium where
frequencies have the same velocity (a
nondispersive medium), we can write

( ) ( )
2 2
2 2 2
, ,
1
x t x t
x v t
c + c +
=
c c
where v = velocity at which the wave propagates
nd
Edition
Example 13.2
The nondispersive wave equation in one dimension
is given by

Show that the traveling wave
is a solution of the nondispersive wave equation.
How is the velocity of the wave related to k and w?
( ) ( )
2 2
2 2 2
, ,
1
x t x t
x v t
c c
=
c c
( ) ( ) | + = wt kx A t x sin ,
nd
Edition
Solution
The nondispersive wave equation in one dimension is given
by

Show that the traveling wave is a
solution of the nondispersive wave equation. How is the
velocity of the wave related to k and w?
( ) ( ) | + = wt kx A t x sin ,
( ) ( )
2 2
2 2 2
, ,
1
x t x t
x v t
c c
=
c c
1 2
( , ) cos( ) ( ) ( )!!! x t A t kx x t e + = + + =
nd
Edition
Example 13.2
We have
( ) ( )
( )
( )
k w v
wt kx A
v
w
t
wt kx A
t
t x
v x
t x
/ gives results two these Equating
sin
sin
, 1 ,
2 2
2
2
2
2
2
=
+
=
c
+ c
c
c
=
c
c
|
|

nd
Edition
13.3 Waves Are Conveniently Represented as Complex
Functions
It is easier to work with the whole complex
function knowing as we can extract the real
part of wave function.
nd
Edition
( )
1 2
( , ) ( ) ( ) sin )cos( x t x t A kx t e + = = +
Standing (stationary) wave
nd
Edition
Example 13.3
a. Express the complex number 4+4i in the
form .
b. Express the complex number in the
form a+ib.
2 / 3
3
t i
e
u i
re
nd
Edition
Solution
a. The magnitude of 4+4i is
The phase is given by

Therefore, 4+4i can be written
4
2
1
cos or
2
1
2 4
4
cos
1
t
u u = = = =

( )( ) | | 2 4 4 4 4 4
2 / 1
= + i i
( ) 4 /
2 4
t i
e
nd
Edition
Solution
b. Using the relation
can be written
( ) i i i 3 0 3
2
3
sin
2
3
cos 3 = =
|
.
|
\
|
+
t t
( )
2 / 3
3 , sin cos exp
t o
o o o
i i
e i i e + = =
nd
Edition
13.2 Some Common Waves (Traveling waves)
( ) ( )
0 0
, cos 2 cos
r r
r t
r t kr t
T
t e
+ + | |
+ = + = +
|
\ .
( )
, sin 2
sin( )
x t
x t A
T
A t kx
t
e
| |
+ =
|
\ .
= + +
Planar wave
Spherical wave
Cylindrical wave
( ) ( )
0
, cos
r
r t kr t e
+
+ = +
( ) ( )
2 2
2 2
, , x t x t
t x
c + c +
=
c c
( )
2
,
( , )
1
( )
2 2
r t
r t
r
r r r
v t
=
c +
c+
c
c c
c
( )
( )
2
2
2
2
2
,
( , ) ( , )
2
2 2
2
( , )
( ( , ))
2 2
r t
r t r t
r r
r
v t
r r t
r r t
r
v t
=
=
c +
c + c+
+
c
c
c
c +
c +
c
c
nd
Edition
13.4 Quantum Mechanical Waves and the Schrdinger
Equation
The time-independent Schrdinger
equation in one dimension is

It used to study the stationary states of
quantum mechanical systems.
( )
( ) ( ) ( ) x E x x V
dx
x d
m
h

= +
2
2 2
2
nd
Edition
Equation
An analogous quantum mechanical form of
time-dependent classical nondispersive wave
equation is the time-dependent Schrdinger
equation, given as

where V(x,t) = potential energy function
This equation relates the temporal and spatial
derivatives of (x,t) and applied in systems
where energy changes with time.
( ) ( )
( ) ( ) t x t x V
x
t x
m
h
t
t x
ih , ,
,
2
,
2
2 2
+ +
c
+ c
=
c
+ c
nd
Edition
Equation
For stationary states of a quantum mechanical
system, we have

Since , we can show that that
wave functions whose energy is independent of
time have the form of
( )
( ) t x E
t
t x
ih ,
,
+ =
c
+ c
( ) ( )
( )t
x t x
E/h -i
e , = +
nd
Edition
13.5 Solving the Schrdinger Equation: Operators, Observables,
Eigenfunctions, and Eigenvalues
We waould need to use operators, observables,
eigenfunctions, and eigenvalues for quantum
mechanical wave equation.
The time-independent Schrdinger equation is
an eigenvalue equation for the total energy, E

where {} = total energy operator or
It can be simplified as
( ) ( ) ( ) x E x x V
x m
h
n n n
=
)
`
+
c
c
2
2 2
2
H
n n n
E H =
n n n
O
.
=
nd
Edition
Eigenequation, eigenfunction, eigenvalue
n n n
O
.
=
The effect of an operator acting on its eigenfunction is the same as
a number multiplied with that eigenfunction.

There may be an infinite number of eiegenfunctions and eigenvalues.
nd
Edition
Example 13.5
Consider the operators . Is the
function an eigenfunction of
these operators? If so, what are the eigenvalues?
Note that A, B, and k are real numbers.
( )
ikx ikx
Be Ae x

+ =
2 2
/ and / dx d dx d
nd
Edition
Solution
To test if a function is an eigenfunction of an
operator, we carry out the operation and see if the
result is the same function multiplied by a
constant:

In this case, the result is not multiplied by a
constant, so is not an eigenfunction of the
operator d/dx unless either A or B is zero.
( )
( )
ikx ikx ikx ikx
ikx ikx
Be Ae ik ikB ikAe
dx
Be Ae d
= =
+

( ) x
( ) x
nd
Edition
Solution
This equation shows that is an eigenfunction
of the operator with the eigenvalue k
2
.
2 2
/ dx d
( ) x
( )
( ) ( ) ( ) ( ) x k Be Ae k B ik Ae ik
dx
Be Ae d
ikx ikx ikx ikx
ikx ikx
2 2
2 2
2
2
= = + =
+


nd
Edition
Matrix as Quantum Mechanical Operator
n n n
O
.
=
1 0 1 0 0 1 0
, , ,
0 1 0 1 1 0 0
i
i
| | | | | | | |
| | | |

\ . \ . \ . \ .
1 0 0 1 0 0 0 1 0 0 0
0 1 0 , 0 0 0 , 1 0 1 , 0
0 0 1 0 0 1 0 1 0 0 0
i
i i
i
| | | | | | | |
| | | |
| | | |
| | | |

\ . \ . \ . \ .
0 1 0 1
1 0 1 0
k k
k k k k
k k
a a
b b

| | | | | | | |
= =
| | | |
\ . \ .\ . \ .
0 1 0 0 1 0
1 0 1 1 0 1
0 1 0 0 1 0
k k
k k k k k k
k k
a a
b b
c c

| | | || | | |
| | | |
= =
| | | |
| | | |
\ . \ .\ . \ .
nd
Edition
Eigenvalues and eigenvector of the Matrix Operator
n n n
O
.
=
2
1 2
1 1 2 2
1 1 2 2
0 1 0 1
1 0 1 0
0 1 0 1
0 det 0
1 0 1 0
(0 ) 1 0 1 1, 1.
0 1 0 1
1 , 1
1 0 1 0
k k
k k k k
k k
k k k
k k k
k k
a a
b b
a
b
a a a a
b b b b

| | | | | | | |
= =
| | | |
\ . \ .\ . \ .

| || | | |
= =
| | |

\ .\ . \ .
= = = =
| | | | | | | | | | | |
= =
| | | | | |
\ . \ . \ . \ . \ . \ .
( ) ( )
1 1 2 2
1 2
1 1 2 2
1 2
1 1 2 2
1 2
1 1
1 1 2 2
2 2
1 1
2 2 1 2
1 1 2 2
1 1
1 2
2 2
1: 1:
Using normality condition: 1, 1
, .
1, , 1, .
b a b a
a b a b
a a
a b a b
b b
a b a b
a a
b b

= =

= =

= =

| | | |
= =
| |
\ . \ .
= = = =
| | | |
| | | |
= = = = = = | |
| |
| |
\ . \ .
\ . \ .
nd
Edition
Exercise
n n n
O
.
=
0 0
0 0
? ?
k k
k k k k
k k
k
k
k
a a i i
b b i i
a
b

| | | | | | | |
= =
| | | |

\ . \ .\ . \ .
| |
= =
|
\ .

http://140.117.34.2/faculty/phy/sw_ding/teaching/chem-math1/cm07.ppt
nd
Edition
Review of Orthogonal decomposition of
vectors and functions:
1 2 3
Vector in 3D space:
Orthogonality: 0, 0, 0,
Normality: 1, 1, 1.
Denoting = , ,
1 if
0 if
x y z
j k jk
A A A
j k
j k
o
= + +
= = =
= = =
= =
= =
= =

= =
V i j k
i j i k j k
i i j j k k
i i j i k i
i i
1 1 2 2 3 3
1
1 2 1 3 2 3 1
1 1 2 2 3 3 1 1
Vector in nD space: ...
Orthogonality: 0, 0,... 0,..., 0.
Normality: 1, 1, 1,..., , 1.
1 if
0 if
n
n n j j
j
n n
n n n n
j k jk
A A A A A
j k
j k
o
=

= + + + + =
= = = =
= = = =
= =
= =
= =
V i i i i i
i i i i i i i i
i i i i i i i i i i
i i

0
0
{ , 0,1, 2, 3... } * = ,
, *
Extend to functions of continuous variables:
{ ( ), 0,1, 2, 3... } * ( ) ( )= ,
( ) ,
m n m nm
n n n n
n
m n m nm
n n
n
m
a a
x m dx x x
x a
| | | o
| |
| | | o
|
=
= ==>
= =
= ==>
=
* ( ) ( )
n n
a dx x x |
=
}
nd
Edition
13.6 The Eigenfunctions of a Quantum Mechanical Operator
Are Orthogonal
Orthogonality is a concept of vector space.
3-D Cartesian coordinate space is defined by

In function space, the analogous expression
that defines orthogonality is
0 = - = - = - z y z x y x
2
* ( ) ( ) | ( ) | 1
i i i
dx x x dx x

= =
} }
0 if
* ( ) ( )
1 if
i j ij
i j
dx x x
i j
o
= =
}
Orthogonormality:
nd
Edition
Example 13.6
Show graphically that sin x and cos 3x are
orthogonal functions. Also show graphically that
( )( ) 1 for 0 sin sin = = =
}

m n dx nx mx
( )( )
sin sin 0 for mx nx dx n m
t
t
= =
}
( )( )
1
2
sin sin 1 for integers. nx nx dx n
t
t
t
= =
}
( )( )
sin cos 0 for any , mx nx dx n m
t
t
=
}
nd
Edition
Solution
The functions are shown in the following
graphs. The vertical axes have been offset to
avoid overlap and the horizontal line indicates
the zero for each plot.
Because the functions are periodic, we can
draw conclusions about their behaviour in an
infinite interval by considering their behaviour
in any interval that is an integral multiple of the
period.
nd
Edition
Solution
nd
Edition
Solution
The integral of these functions equals the sum
of the areas between the curves and the zero
line. Areas above and below the line contribute
with positive and negative signs, respectively,
and indicate that and
. By similar means, we could
show that any two functions of the type sin mx
and sin nx or cos mx and cos nx are orthogonal
unless n=m. Are the functions cos mx and sin
mx(m=n) orthogonal?
( )( ) 0 3 cos sin =
}

dx x mx
( )( ) 0 sin sin >
}

dx x x
nd
Edition
Are Orthogonal
3-D system importance to us is the atom.
Atomic wave functions are best described
by spherical coordinates.
0 if
* ( ) ( )
1 if
0 if
* ( , , ) ( , , )
1 if
0 if
sin * ( , , ) ( , , )
1 if
i j ij
i j ij
V
i j ij
V
i j
dx x x
i j
i j
dxdydz x y z x y z
i j
i j
r drd d r r
i j
o
o
u u u u o
= =

=
= =

=
= =

=
}
}}}
}}}
nd
Edition
Example 13.8
Normalize the function over the interval

Solution:
Volume element in spherical coordinates is
, thus
r
e
t | t u 2 0 ; 0 ; 0 s s s s s s r
| u u d drd r sin
2
1 4
1 sin
0
2 2 2
0
2 2
0
2
0
2
=
=
}
} } }
dr e r N
dr e r d d N
r
r
t
u u |
t t
nd
Edition
Solution
Using the standard integral ,

we obtain
The normalized wave function is

Note that the integration of any function involving
r, even if it does not explicitly involve ,
requires integration over all three variables.
r
e
r
e
t
1
( ) integer positive a is , 0 / !
0
1
n a a n dx e x
n ax n
> =
}
+
t
t
1
that so 1
2
! 2
4
3
2
= = N N
u | or
nd
Edition
Form a Complete Set
The eigenfunctions of a quantum mechanical
operator form a complete set.
This means that any well-behaved wave
function, f (x) can be expanded in the
eigenfunctions of any of the quantum
mechanical operators.
13.4 Expanding Functions in Fourier Series
0
( ) , * ( )
n n n n
n
x a a dx x | |
=

= =
}
nd
Edition
Form a Complete Set
Fourier series graphs
nd
Edition
Fourier series

cos nx

0,1, 2, n =
sinnx

1, 2, 3, n =
cos cos 0 mx nxdx
t
t
+
=
}

m n =
sin sin 0 mx nxdx
t
t
+
=
}

m n =
cos sin 0 mx nxdx
t
t
+
=
}

, all m n
2 , 0
cos cos
, 0
if n
nx nxdx
if n
t
t
t
t
+
>
}

sin sin nx nxdx
t
t
t
+
=
}

0 if n >
0
1 2 3
1 2 3
0
1
( ) cos cos 2 cos3
2
sin sin 2 sin3
( cos sin )
2
n n
n
a
f x a x a x a x
b x b x b x
a
a nx b nx
=
= + + + +
+ + + +
= + +
1
( ) cos
n
a f x nxdx
t
t
t
+
=
}
1
( )sin
n
b f x nxdx
t
t
t
+
=
}
nd
Edition
The function f(x) (blue line) is approximated by the summation of
sine functions (red line):
0
1 2 3
1 2 3
0
1
( ) cos cos 2 cos3
2
sin sin 2 sin3
( cos sin )
2
n n
n
a
f x a x a x a x
b x b x b x
a
a nx b nx
=
= + + + +
+ + + +
= + +

nd
Edition
Fourier Transforms (FT)

| |
0
( ) ( ) cos ( ) sin f x u y xy y xy dy u
= +
}
1
( ) ( ) cos u y f x xydx
t
+
=
}
1
( ) ( )sin y f x xydx u
t
+
=
}
nd
Edition
FT in exponential form

1
cos ( )
2
ixy ixy
xy e e
= +
1
sin ( )
2
ixy ixy
xy e e
=
| |
1
( ) ( ) ( )
2
w y u y i y u =
( ) ( )
ixy
f x w y e dy
+
=
}
1
( ) ( )
2
ixy
w y f x e dx
t
+

=
}
| |
0
( ) ( ) cos ( ) sin f x u y xy y xy dy u
= +
}
1
( ) ( ) cos u y f x xydx
t
+
=
}
1
( ) ( )sin y f x xydx u
t
+
=
}
nd
Edition
For students who are not familiar with orthogonal
expansion of functions, you may find the following ppt
tutorial helpful:
http://140.117.34.2/faculty/phy/sw_ding/teac
hing/chem-math1/cm07.ppt

You should also read a chemistry math book and do some exercises
for better understanding.

Erpc Chapter13

Hochgeladen von

Dokumentinformationen

Originalbeschreibung:

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Erpc Chapter13

Hochgeladen von

Copyright:

Verfügbare Formate

Physical Chemistry 2

2010 Pearson Education South Asia Pte Ltd

2010 Pearson Education South Asia Pte Ltd

Das könnte Ihnen auch gefallen