,
Professor Robert W. Field
: At the start of Lecture on Friday , October 18.
: 1. 2. A. Use the
a
,
a
† algebra introduced at the end of Lecture #13 to organize the matrix elements of
x
3 and
x
4 according to selection rules: B .

x
3 
+ 3

x
3 
+ 1

x
4 
+ 4

x
4 
+ 2

x
4 
Use nondegenerate perturbation theory to express the energy levels of
=
x
2 /2 +
x
3 +
x
4
=
0 /
+ ω
e
(
+ / ) ± ω
e
e
(
+ 1 2 + ω
e
e
(
+ / ) 3 where ω e , ω
e
e
, and ω
e
e
are traditional vibrational constants. Express E 0 , ω
e
, ω
e
e
, and algebra. ω
e
e
in terms of
,
,
, and
. This is an extremely complicated and tedious algebraic nightmare. Maybe you can get your computer to do the You are going to approach the following potential energy curve using a variety of methods , including the Discrete Variable representation (DVR) and Perturbation Theory: V(
) = k
x
2 /2 – a
x
3 + b
x
4 . When 
 > [(16/9)kb] 1/2 , V(
) has two minima , at x min1 = 0 [V(0) = 0] and
min 2 =
+ 9
2 − 16

] 1/2
Chemistry 5.73 Problem Sets #5 and a maximum at
max =
− 9
2 − 16

] 1/2 .
3. Page 2 When 
 < [(16/9)kb] 1/2 the second minimum disappears. Let
= 1.000 × 10 –2
= 1.000 × 10 4 
 = 1980 
 = 200 in appropriate units. A. B . C. Find the energy of the local maximum of V( number of levels that
) , V(
max ) , and use the WKB quantization condition to find the total number of bound levels at energy below the top of the potential hump. Also use WKB quantization to estimate the would bind at
≤ V(
max ). Use DVR to solve for the energies of the lowest
levels of this well , where
is twice the total number of levels bound below V(
max ). Use a 500 × 500
x
matrix. Use the expectation value of
to apportion the levels you found below V(
max ) into those bound primarily in the left (deeper) well and those bound in the right (shallower) well. Note that you can use the eigenvectors from DVR (because these are expressed in the harmonic oscillator basis set) to calculate
for each eigenstate. D. Fit the 5 lowest energies of those levels that you found in part C to be localized in the left (deeper) well to a power series in
+ 1/2 ( )
0
+ ω
e
(
+ 1 2
e
e
(
+ 1 2 + ω
e
e
(
+ 1 2 3 where ω e , ω e
e levels below V( ,
and max ω e
e are the traditional names for the vibrational expansion coefficients. Note that if you had attempted to fit a l l of the energy ) to this sort of power series , you would have required many more constants to obtain an acceptable fit and the fitted values of ω e , ω e x e , and ω e y e would not agree well with the values from perturbation theory. Compare the results you obtained in 1B to those you obtained in 2D. E. Return to Problem #2 on Problem Set #3 , using perturbation theory this time. V 1 (x) = ∞ x > L/2 V 2 (x) = a[ δ (x – L/6) + δ (x + L/6)] Let
H
E ( ) ( ) n = =
P
2 h 2 2m + V 1 x n 2 n = , , … ψ ( ) n = [2 /L] 1/2 cos [ n π ( x + L/2 ) /L ]
H
( ) = ( )
Chemistry 5.73 Problem Sets #5 Page 3 A. B . C. D. E. Find the first order corrections to all of the energy levels. Comment on the three classes of states with respect to their values of E the sign of a? n . Do the E n depend on Before you derive the secondorder corrections to all of the energy levels it is necessary to consider the selection rules on n
H
( ) m . What are these selection rules? Work out the E n sign of a? secondorder energy corrections. Do the E ( ) n 2 depend on the Use perturbation theory to address the question of when there will be zero and when there will be only one level at E < 0. Reconsider the twosided correlation diagram proposed in 2E of Problem Set #3. Show that , for the three classes of levels , the energy levels are described by E n = E ( ) n + aA n + a 2 B n .
For which classes of levels is A n = 0? For which classes of levels is B n = 0?