Spectroscopy of Molecular Rotation in Gases and Liquids

Author： A. I. Burshtein; S. I. Temkin

Publisher： Cambridge University Press‎

Publication year： 1994

E-ISBN: 9780511884788

P-ISBN(Paperback): 9780521454650

Subject： O561.3 molecular spectroscopy

Keyword：化学原理和方法

Language： ENG

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Spectroscopy of Molecular Rotation in Gases and Liquids

Description

Spectroscopic studies can reveal a wealth of information about the rotational and vibrational behaviour of the constituent molecules of gases and liquids. This 1994 book reviews the fundamental concepts and important models which underpin such studies, dealing in particular with the phenomenon of spectral collapse, which accompanies the transition from rare gas to dense liquid. Throughout, discussion of the various quantum mechanical and semiclassical theories is interwoven with analysis of experimental results. These include data from optical, NMR, ESR and acoustic investigations. The book concludes with a discussion of the latest theories describing the mechanism of rotational diffusion in liquid solutions. This comprehensive review of theoretical models and techniques will be invaluable to graduate students and researchers interested in molecular dynamics and spectroscopy.

Chapter

1 Rotational relaxation

1.1 The Feller equation

1.2 Adiabatic relaxation

1.3 The Keilson-Storer kernel

1.4 Non-adiabatic relaxation

1.5 General solution of the Feller equation

1.6 Angular momentum correlation functions

1.7 Impact processes with finite collision time

1.8 The memory function formalism

1.9 Non-Markovian differential theory

1.10 Rotational kinetics and relaxation time

2 Orientational relaxation in dense media

2.1 Correlation characteristics of rotational relaxation

2.2 Stochastic perturbation theory

2.3 Rotational diffusion

2.4 Reorientation in the impact approximation

2.5 Finite collision time

2.6 Cumulant expansion

3 Transformation of isotropic scattering spectra

3.1 Static contour

3.2 Perturbation theory

3.3 The impact theory of frequency exchange

3.4 Transformation of the contour by strong collisions

3.5 Transformation of the contour by weak collisions

3.6 Comparison with experiment: linear molecules

3.7 The Q-branch band shape in the Keilson-Storer model

3.8 Comparison with experiment: spherical molecules

4 Quantum theory of spectral collapse

4.1 Spectral exchange in impact theory

4.2 Collapse of the spectral doublet

4.3 Non-Markovian binary theory

4.4 Line interference in stochastic perturbation theory

4.5 Impact theory of rotational spectra

4.6 Collapse of isotropic Raman spectra

5 Rotational relaxation: kinetic and spectral manifestations

5.1 The impact operator in semiclassical theory

5.2 Correction for detailed balance

5.3 Angular momentum and energy relaxation

5.4 Calculation methods

5.5 Experimental verification of SCS calculated rates

5.6 Broadening and collapse of the isotropic Q-branch

5.7 The fitting laws

6 Impact theory of orientational relaxation

6.1 Interference of rotational branches in molecular spectra

6.2 The quasi-static approximation

6.3 Approaches of weak and strong collisions

6.4 Orientational relaxation times

7 Rotation and libration in a fluctuating cell

7.1 The fluctuating cell model

7.2 Kinetic equation of the model

7.3 General solution

7.4 Anticorrelated perturbation

7.5 Non-correlated perturbation

7.6 The Hubbard relation in the frames of the liquid cage model

Appendix 1

Appendix 2

Appendix 3

Appendix 4

Appendix 5

Appendix 6

Appendix 7

Appendix 8

Appendix 9

References

Index

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