CHEM F111 General Chemistry Quantum Description of Some Simple Systems

BITSPilani, Pilani Campus
CHEM F111 General Chemistry

Lecture 10
Quantum description of some simple systems

BITS Pilani
Pilani Campus
30-August-2013
1
Quantum Theory
Review of Lecture 9
2
30-August-2013
2
Wavefunction: Probability Amplitude
Square of the wavefunction: Probability Density

Operator
Hamiltonian Operator (Total Energy)

Eigen value equation
Schrdinger equation for stationary states

Particle in one dimension box

(
+
|
|
.
|
\
|
c
c
+
c
c
+
c
c
= ) (
2
2
2
2
2
2
2 2
r V
z y x m
H

= E
Particle in one dimensional box
30-August-2013
3
V(x) = 0
|
.
|
\
|
= x
L
n
L
x
n
t
sin
2
) (
n = 1, 2, .

E =
n
2
h
2
8mL
2
(
2
/2m) d
2
(x)/dx
2
=
|
.
|
\
|
x
L
n
L mL
h n t
sin
2
8
2
2 2
= E
How do the wavefunctions look like?
30-August-2013
4
( )
|
.
|
\
|
=
L
x n
L
x
n
t
sin
2
n = 1, 2, .

-
E
Energy is quantized

E =
n
2
h
2
8mL
2
n = 1, 2,
= 2L/n; where n = 1,2,3,
(n 1) nodes in
n

Zero point energy
30-August-2013
5
Free Electron Models
R
R
L
6 t electrons
HOMO
LUMO
AE
2 2
2
8
n
n h
E
mL
=
2 2 2
2
8
L H
n n h
E
mL
(

A =
2 2
1 2 1
L H L H H
n n n n n = + = +
2
2
2 1
8
H
n h
E
mL
( +

A =
Particle in two dimensional box
30-August-2013
6
A two-dimensional
square well.
Potential energy is
zero between x = 0
and x = L
1
and y= 0
and y = L
2
,
Rises sharply to
infinity at the walls.
The Schrdinger equation
0
2
2 2
2
2
2
=
|
.
|
\
|
+
|
|
.
|
\
|

+
mE
dx
d
dx
d
( )
|
|
.
|
\
|
t
=
1 1
2
L
x n
sin
L
x X
x
( )
|
|
.
|
\
|
t
=
2 2
2
L
x n
sin
L
y Y
y
Separation of variables leads to

nx,ny
(x,y) = X
nx
(x) Y
ny
(y)
30-August-2013
7
X(x) = E
x

Y(y) = E
y

E= E
x
+ E
y

E = E
x
+ E
y

E
nx,ny
= n
x
2
h
2
/8mL
1
2
+ n
y
2
h
2
/8mL
2
2
= (n
x
2
/L
1
2
+ n
y
2
/L
2
2
)h
2
/8m
Where n
x
= 1,2,3.; n
y
=1,2,3
30-August-2013
8
|
|
.
|
\
|
|
|
.
|
\
|
=
2 1 2 1
sin sin
2 2
) , (
L
y n
L
x n
L L
y x
y
x
t
t

Particle in two dimensional box (Square)
Now, when L
1
= L
2
E
nx,ny
= n
x
2
h
2
/8mL
2
+ n
y
2
h
2
/8mL
2
= (n
x
2
+ n
y
2
)h
2
/8mL
2
where n
x
= 1,2,3; n
y
=1,2,3

30-August-2013
9
E
1, 1
E
2, 1
E
1, 2
E
2, 2
E
3, 1
E
1, 3
Doubly Degenerate states
2-fold degenerate
Doubly Degenerate states
2-fold degenerate
Non Degenerate state
Non Degenerate state
Degeneracy
Write the four wavefunctions of a cubical box of length L that have
energy of 27(h
2
/8mL
2
).

30-August-2013
10

( , , ) ( ) ( ) ( )
x y z
H x y z H H H x y z
(
+ = + +

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

E = n
x
2
h
2
/8mL
2
+ n
y
2
h
2
/8mL
2
+ n
z
2
h
2
/8mL
2
= (n
x
2
+ n
y
2
+ n
z
2
)h
2
/8mL
2
find the various values of nx, ny and nz such that
n
x
2
+ n
y
2
+ n
z
2
= 27

Degeneracy
Using the combinations of quantum numbers (3,3,3), (5,1,1), (1,5,1) and
(1,1,5) in the particle in a 3D box wavefunctions:

30-August-2013
11
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
=
L
z
L
y
L
x
L L L
t t t
3
sin
3
sin
3
sin
2 2 2
) 3 , 3 , 3 (
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
=
L
z
L
y
L
x
L L L
t t t
1
sin
1
sin
5
sin
2 2 2
) 1 , 1 , 5 (
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
=
L
z
L
y
L
x
L L L
t t t
1
sin
5
sin
1
sin
2 2 2
) 1 , 5 , 1 (
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
=
L
z
L
y
L
x
L L L
t t t
5
sin
1
sin
1
sin
2 2 2
) 5 , 1 , 1 (
30-August-2013
12
Vibrational motion
Turning Points, A, -A
m
Hooke's Law
F k x = linear restoring force
spring constant
force
Harmonic oscillator - oscillates sinusoidally.
A is how far the spring is stretched initially.
At the turning points, A, -A, motion stops.
All energy is potential energy.
30-August-2013
13
Vibrational motion
Classical Mechanics
V
x

Potential is Parabolic
( ) V x
F
x
c
c
=
2
1
( )
2
V x k xdx k x = =
}
Energy of oscillator is
2
1/ 2 E kA =
A can take on any value. Energy is
continuous, continuous range of values.
A - classical turning point.
Turning point
Kinetic energy
zero; potential
energy max.
Classical particle can never be past turning point.
Particle can be stationary at bottom of well,
know position, x =0; know momentum, p = 0.
This can't happen for Q.M. harmonic oscillator.
Uncertainty Principle indicates that minimum Q.M. H.O. energy
30-August-2013
14
The Quantum Mechanical Harmonic Oscillator

= E
E kx
x d
d
m
=
(
+
2
2
2 2
2
1
2
Wavefunctions
( )
2
2

y
v v v
e y H N

=
H
v
- Hermite Polynomials

v vibrational quantum number
4
1
2
)
`
= o
o
=
mk
;
x
y

kinetic energy potential energy
2
2
2 2
2
1
2
kx
x d
d
m
+ = H

Solve the Schrodinger equation and apply the boundary conditions
( 0 as x ) to get:
30-August-2013
15
Total Energy: Eigen value

Eigenvalues:
2 / 1
,... 2 , 1 , 0 ;
2
1
|
.
|
\
|
=
=
|
.
|
\
|
+ =
m
k
E
e
v e v
v

The energy of the oscillator depends
v vibrational quantum number
The force constant k
Particle mass m
30-August-2013
16
Quantum Mechanical Harmonic Oscillator
Wavefunction

The normalized wavefunction and probability distribution (shown also by
shading) for the lowest energy state and first excited state of a harmonic
oscillator.
30-August-2013
17
The first five normalized wavefunctions of the QM harmonic oscillator
Quantum Mechanical Harmonic Oscillator
Wavefunction

30-August-2013
18
The Probability Distributions

Note regions of
highest probability
move towards the
turning points of the
classical motion as v
increases.
30-August-2013
19
Compare with Classical Harmonic Oscillator

Classical mechanics
Quantum mechanics
2 / 1
,... 2 , 1 , 0 ;
2
1
|
.
|
\
|
=
=
|
.
|
\
|
+ =
m
k
E
e
v e v
v

2
( ) sin( ), =
1
2
k
x t A t
m
E kA
e e =
=
Amplitude (A) can take
any arbitrary value, so
energy is not quantized
Quantum
number
E
0
=
1
2

Zero-point energy
30-August-2013
20

classical turning points

wavefunction extends into classically
forbidden region. (Tunneling)
30-August-2013
21

Quantum-mechanical harmonic oscillator serves as the basic
model for molecular vibrations. Its solutions are characterized by
(a) uniform energy separation,
(b) zero-point energy,
(c) larger probability at turning points.
Greater probability
near the turning
points. Again
correspondence to
classical case.
30-August-2013
22
Rotation: particle on a ring
Particle constrained to move on a ring of radius r.
Entire energy is kinetic
The potential energy is constant and can be taken
to be zero (as it is unchanged during rotation).
30-August-2013
23
Angular Momentum of a Particle Confined
to a Plane
Magnitude is represented by a
vector of length |m
l
| units along
the z-axis

Orientation that indicates the
direction of motion of the
particle.

What are the variables?
Angle:
What should be the form of
Hamiltonian?
= KE + PE

= L
2
z /2I
The angular momentum operators
are written as follows
| c
c
= i L
z
) (
) (
2
) (
) ( 1
2
2
2 2
2
2
2
2
|
|
|
|
|
|
E
I
E
r m
=
c
c
=
c
c
|
30-August-2013
24
Particle on a ring: Boundary Conditions
How the boundary condition
should be?
should have a period of 2,
hence
() = (2 + )
A cyclic boundary condition
Cyclic boundary condition should be
n = 2tr
n = 0, 1, 2, 3,.
30-August-2013
25
Particle on a ring: wavefunctions
The normalized general solutions:

have to fulfill the cyclic boundary condition (|)= (|+2t):
( )
2 / 1
2
) (
t
|
|
l
im
e
=
( ) ( )
) (
2 2
) 2 (
2
2 / 1
2
2 / 1
) 2 (
|
t t
t |
t
t | t |
l
l l l
m i
m i im im
e
e e e
= = = +
+
( ) ( ) ( ) 1 1 sin cos
2 2
2
2
= = + = =
l l
l
l
m m
m
i m i
i e e t t
t t
2m
l
= an even integer m
l
= 0, 1, 2, 3, ...
I
m
I
L
E
l z
2 2
2 2 2
= =
The eigenvalues are given by
With m
l
2
, the energy does not depend on the sense of rotation

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CHEM F111 General Chemistry

BITSPilani, Pilani Campus

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