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http://ocw.mit.edu 5.80 SmallMolecule Spectroscopy and Dynamics
Fall 2008 For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms. MASSACHUSETTS INSTITUTE OF TECHNOLOGY Chemistry 5.76 Spring 1977 Problem Set #1
Due February 14, 1977
1. Carry out the angular momentum algebra indicated in Section 2 (of Steinfeld, Chapter 1); that is,
��
�
�
show explicitly that 11z j x 11z = 0, and that J2 − �J x �2 � 0.
x
2. (a) Given the matrix elements of the coordinate x for a harmonic oscillator:
�
�
ψ� xψv� d x = 0 unless v� = v ± 1
�vxv � =
v
and
�v + 1xv� = (2β)−1/2 (v + 1)1/2
�v − 1xv� = (2β)−1/2 (v)1/2
where β = 4π2 mω/h, and ω is the vibrational frequency. Evaluate the nonzero matrix elements of x2 , x3 , and x4 ; that is, evaluate the integrals �
r�
ψv xr ψv� d x
�vx v � =
for r = 2, 3, and 4 (without actually doing the explicit integrals, of course!).
(b) From the results of (a), evaluate the average values of x, x2 , x3 , and x4 in the vth vibrational
state. Is it true that x2 = ( x)2 , or that x4 = ( x2 )2 ? What conclusions can you draw about the
results of a measurement of x in the vth vibrational state? 3. Let �
�H11 0 0 �
�
�
�
�
�
H = � 0 d V �
in the φi basis, and
�
�
�
�
� 0 V −d �
�
�
�1
0
0�
�
�
�
�0 cos θ − sin θ�
�
U = �
�
� �0 sin θ cosθ �
�
�
�1/2
� �1/2
d d
cos θ = 1/2 +
sin θ = 1/2 −
2(d2 + V 2 )1/2
2(d2 + V 2 )1/2 (a) Calculate U† HU. Problem Set #1 Spring, 1977 Page 2 (b) List the three energy eigenvalues and associated eigenfunctions expressed as the linear combi
nations of the φi basis functions.
(c) Show that the eigenfunctions are normalized and mutually orthogonal.
(d) Suppose that µ is the electric dipole transition moment operator, and that its matrix represen
tation in the φi basis is �
� 0 µ12 µ13 �
�
�
�
�
�
�µ12 0
0 � . µ=�
�
�
�
�µ13 0
0 �
Express µ in the energy eigenbasis. (e) What are the transition probabilities between energy eigenstates, expressed in terms of µ12 , µ13 ,
V , d, and H11 ?
(f) There are several interesting limiting cases. Suppose φ2 and φ3 are “unperturbed” states which
have equal transition probabilities, µ12 2 = µ13 2 , from φ1 . V is a perturbation term which
causes φ2 and φ3 to mix. The U23 and U32 elements are the mixing coeﬃcients.
(i) Let d/V  � 1. The perturbation is turned oﬀ. What are the ψ1 → ψ2 and ψ1 → ψ3
transition probabilities?
(ii) Let d/V  � 1. The perturbation is on full strength. What are the ψ1 → ψ2 and ψ1 → ψ3
transition probabilities? Note that one transition has accidentally become forbidden, even
though the ﬁnal state is composed of equal parts of two basis functions, each of which
have allowed transitions from φ1 = ψ1 . This is a quantum interference eﬀect that is often
observed experimentally.
(iii) Let d > 0, V > 0, and µ12 = µ13 . Which transition is allowed, the one to the upper or
lower of the mixed levels?
(iv) Note that if µ12 = −µ13 , the opposite transition becomes allowed. What happens when the
sign of V is switched? What happens when the sign of d changes? Answer in terms of
transitions to upper vs. lower eigenstates rather than ψ2 or ψ3 .
(v) Comment on when changing the sign of an oﬀdiagonal matrix element might be expected
to have observable consequences.
4. Several methods for computer diagonalization of large matrices are discussed in the handout “Notes
on matrix Methods” pages 12–18. Unfortunately there are several typographical errors.
(a) What is the error in Equation 3.10?
(b) The discussion of Method IIB is rather confused. Describe the procedure for construction of
a tridiagonal matrix. Which matrix element is annihilated ﬁrst? How does the rotation diﬀer
from that performed in Method IIA? Why is it possible to arrange for annihilation of various
elements without spoiling any of the previously zeroed oﬀdiagonal elements? Why is it not
possible to reduce the matrix beyond tridiagonal form?
(c) Suppose you have a 5 × 5 tridiagonal matrix and apply Method IIA to annihilate the M34 and
M43 elements. What happens to the elements outside of the 2 × 2 (3, 4) block? ...
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This note was uploaded on 11/28/2011 for the course CHEM 5.74 taught by Professor Robertfield during the Spring '04 term at MIT.
 Spring '04
 RobertField
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