Beruflich Dokumente
Kultur Dokumente
Objectives
Solving Schrdinger Equation
Introducing Angular Momentum
Introducing Spherical Harmonic
Functions
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Outline
1. Solving the Schrdinger Equation for the
Quantum Mechanical Harmonic
Oscillator
2. Solving the Schrdinger Equation for
Rotation in Two Dimensions
3. Solving the Schrdinger Equation for
Rotation in Three Dimensions
4. The Quantization of Angular Momentum
5. The Spherical Harmonic Functions
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
2
x An H n x e
, and n 0,1,2,...
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Example 18.1
x 2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Solution
We have
h 2 d 2 n ( x)
V x n x En n x
2
2 dx
2
x 2
h d e
2 dx 2
V x e h d 2xe 1 kx e
2
dx
2
x
x 2
x 2
h2
h2
1 2 x 2
x 2
2 2 x 2
2 xe
4 x e
kx e
2
2
2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Solution
The function is an eigenfunction of the
total energy operator only if the last two
terms cancel:
H total e x
h 2 x 2
1 k
2
e
if
4 h2
Finally,
h2 h2
E
1 k h k
2
4h
2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
1 x
2 x
1/ 4
xe 1/ 2 x
1/ 4
1/ 4
1/ 4
3 x
9
e 1 / 2 x
2x
2x
1 e 1 / 2 x
3x e
1 / 2 x 2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
n hv n with n 1,2,3,...
2
2
1
2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Example 18.2
x 4 3 / 4 xe 1/ 2 x
a. Is
an eigenfunction of the
kinetic energy operator? Is it an
eigenfunction of the potential energy
operator?
b. What are the average values of the kinetic
and potential energies for a quantum
mechanical oscillator in this state?
1
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Solution
a. Neither the potential energy operator
nor the kinetic energy operator commutes
with the total energy operator. Therefore,
x 4 / xe
because
is an eigenfunction of the
total energy operator, it is not an
eigenfunction of the potential or kinetic
energy operators.
3
1/ 2 x 2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Solution
b. The fourth postulate states how the
average value of an observable can be
calculated. Because
then
2
2
h
d
E potential ( x) V ( x) and E kinetic ( x)
2 dx 2
1/ 4
1 4
k
2
xe
1 / 2 x 2
1/ 2
4
dx k
1 2
kx
2
4 x
x
e
1/ 4
xe
(1 / 2 )x 2
dx
4 x
x
e dx
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Solution
The limits can be changed as indicated in the
last integral because the integrand is an
even function of x. To obtain the solution, the
following standard integral is used:
1 3 5 2n 1
2 n x
dx
2 n 1 a n 1
h
potential
a 4 2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Solution
Thus
Ekinetic
h d2
1 x dx
x
2
2 dx
4 3
*
1
1/ 4
xe 1/ 2 x
h 2 4 3
1/ 2
h 4
1/ 2
h2 d 2
2
2 dx
4 3
1/ 4
xe 1/ 2 x dx
2
x 4 3x 2 e x dx
h 4 3
2
2
x 3x e
4 2
x 2 dx
1/ 2
3 h 2 3
k
h
4
4
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Solution
In general, we find that for the nth state,
Ekinetic ,n E potential ,n
h k
1
n
2
2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Example 18.3
The bond length for H19F is 91.68 10-12
m. Where does the axis of rotation
intersect the molecular axis?
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Solution
If xH and xF are the distances from the axis of
rotation to the H and F atoms, respectively,
12
x
91
.
68
10
F
we canH write
and
xHmH=xFmF. Substituting mF=19.00 amu and
mH=1.008 amu, we find that xF=4.5810-12
m and
xH=87.10 10-12 m. The axis of rotation is
very close to the F atom. This is even more
pronounced for HI or HCl.
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
The eigenfunction
the angle .
depends only on
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Example 18.4
A
Determine the normalization constant
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
in
Solution
The variable can take on values between 0
and 2. The following result is obtained:
2
ml ml d 1
0
A e
2
iml iml
d A
d 1
0
1
A
2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
for ml 0,1,2,3..
2
2 r0
2l
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
iml
ml h iml
ih
de
l
e ml h
z
2 d
2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
ly ih z x
z
x
lz ih x y
x
y
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
l ih
z
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
l , l ihl
l , l ihl
l , l ihl
for ml 0,1,2,3,...,l
1 iml
e
ml h ,
2
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Y00 ,
3
Y ,
1/ 2
cos
0
1
5
Y ,
16
1
1
5
Y ,
3 cos
1/ 2
1
2
15
Y ,
32
1
2
sin e i
1/ 2
5
Y ,
16
0
2
1/ 2
sin cos e i
1/ 2
sin 2 e i
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
1 1
3
1
px
Y1 Y1
sin cos
4
2
1
3
py
Y11 Y11
sin sin
4
2i
p z Y10
3
cos
4
d z 2 Y10
3 cos 2 1
16
d xz
1 1
Y2 Y21 415 sin cos cos
2
d yz
1
Y21 Y21 415 sin cos sin
2i
d x2 y2
d xy
1
Y22 Y22 a156 sin 2 cos 2
2i
1
Y22 Y22 1615 sin 2 sin 2
2i
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd
Chapter 18: A Quantum Mechanical Model for the Vibration and Rotation of Molecules
Physical Chemistry 2nd Edition
2010 Pearson Education South Asia Pte Ltd