Selection rules in the dipole approximation are determined by the integral μ mn x = «Ï *

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Selection rules in the dipole approximation are determined by the integral μmnx=  ˆ«Ïˆ*m(Ï„) μx(Ï„) ψn(Ï„) dÏ„. If this integral is nonzero, the transition will be observed in an absorption spectrum. If the integral is zero, the transition is €œforbidden€ in the dipole approximation. It actually occurs with low probability because the dipole approximation is not exact. Consider the particle in the one-dimensional box and set μx= ˆ’e x. 

a. Calculate μ12 x and μ15 x in the dipole approximation. Can you see a pattern and discern a selection rule? You may need to evaluate a few more integrals of the type μ 1m x. The standard integral

axsin - 1)7x (п — 1)л 2 cos (n – 1)TX a co- лх . плх Xsın sin- dx = a a. (п - 1?л? co (n + 1)Tx (п + 1)л

is useful for solving this problem.

b. Determine the ratio μ 12 x / μ 14 x. On the basis of your result, would you modify the selection rule that you determined in part (a)?

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Physical Chemistry

ISBN: 978-0321812001

3rd edition

Authors: Thomas Engel, Philip Reid

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