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Chapter 26: Problem 8

Discuss selection rules for electronic abosorption spectroscopy.

Short Answer

Expert verified
Selection rules for electronic absorption spectroscopy are guidelines that predict allowed and forbidden transitions. The main rule is the Laporte rule that allows changes in orbital type, but for centrosymmetric molecules, it forbids transitions within a given set. The spin rule allows transitions that do not change the spin quantum number. Violations may occur due to other factors.

Step by step solution

01

Understanding Selection Rules

Selection rules in quantum mechanics are guidelines for determining the likelihood of a transition between two energy states. In other words, they help predict the transitions that are allowed (or forbidden) in a quantum system based on its properties like spin and parity.
02

Role of Selection Rules in Spectroscopy

In absorption spectroscopy, an external electromagnetic field (e.g., light) is used to promote electrons from a lower energy level to a higher energy level. The selection rules predict which transitions are likely to occur under certain conditions, thereby helping in the analysis and interpretation of a spectrum.
03

Selection Rules for Electronic Absorption Spectroscopy

In electronic absorption spectroscopy, the key selection rule is the Laporte rule, which says that electronic transitions that involve a change in orbital type (such as from a 's' to a 'p' orbital or from a 'd' to a 's') are allowed. Furthermore, if the molecule is centrosymmetric, transitions within a given set of 'p' or 'd' orbitals are forbidden. Another rule is the spin selection rule, which says that transitions are only allowed if they do not involve a change in the total spin quantum number. However, these are idealized rules and violations can occur due to various factors like spin-orbit coupling and vibronic interactions.

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