1. Absorption of Infrared Radiation by Molecules. Theoretical considerations. Selection rules for infrared absorption. Experimental determination of infrared intensities. 2. Coordinates in Vibrational Analysis.3. Semi–Classical Models of Infrared Intensities. Introduction. Rotational corrections to dipole moment derivatives. The bond moment model. 4. Molecular Dipole Moment Derivatives as Infrared Intensity Parameters. Atomic polar tensors (APT). Bond charge tensors. Bond polar parameters. Effective bond charges from rotation–free atomic polar tensors. 5. Relationship between Infrared Intensity Formulations 6. Parametric Formulations of Infrared Absorption Intensities of Overtone and Combination Bands. Introduction. Anharmonic vibrational transition moment. The charge flow model. The bond moment model. 7. Ab Initio Mo Calculations of Infrared Intensities. Introduction. Computational methods. Calculated infrared intensities. Conclusions. 8. Intensities in Raman Spectroscopy. Molecular polarizability. Intensity of Raman line. Raman intensities and molecular symmetry. Resonance Raman effect. Experimental determination of Raman intensities. 9. Parametric Models for Interpreting Raman Intensities. Rotational corrections to polarizability derivatives. Valence–optical theory of Raman intensities. Atom dipole interaction model (ADIM). Atomic polarizability tensor formulation (APZT). Relationship between atomic polarizability tensors and valence optical formulations of Raman intensities. Effective induced bond charges from atomic polarizability tensors. 10. Ab Initio Calculations of Raman Intensities. Computational Methods. Calculated Raman intensities. References. Author index. Subject index.
The current volume is a single topic volume on the vibrational intensities in the infrared and Raman spectra. Vibrational intensities in infrared and Raman spectra are important physical quantities that are directly related to the distribution and fluctuations of electric charges in the molecule. These spectral parameters can be experimentally determined with good accuracy for many molecules. Additionally, infrared and Raman intensities are presently estimated theoretically by advanced analytical derivative ab initio molecular orbital methods. These fundamental molecular quantities are being used in structural, and other studies, on a limited basis.
Features of this book
- Presents in a systematic way, the theoretical approaches that are used in analyzing and predicting vibrational intensities
- The formalisms developed are illustrated with detailed numerical examples
- Most of the theoretical models described were obtained and then applied to chosen molecules
- A consistent notation is used in presenting the different theoretical approaches, thus eliminating another barrier in understanding some methods, especially those developed by the Russian spectroscopic school.
- No. of pages:
- © Elsevier Science 1996
- 22nd November 1996
- Elsevier Science
- eBook ISBN:
@qu:The appearance of this new survey of the theoretical aspects of vibrational intensities is timely and particularly to be welcomed since the authors have made important contributions to the subject themselves and are also well-placed to interpret the Russian work to spectroscopists in the West. The reader is led through the maze of theoretical models with the welcome help, on the one hand, of a consistent notation for the many matrix equations involved and on the other, of many detailed numerical examples involving simple molecules. Particularly, valuable is the clear exposition of the interrelations of the various approaches.
The authors emphasize both the current and future value in the data obtainable from quantum-mechanical calculations and the need to interpret the primary material which the latter produce, the derivatives of the molecular dipole moment and polarisability with respect to Cartesian atomic coordinates, which is surely the way forward for the subject. @source:Spectrochimica Acta Part A
Sofia University, Sofia, Bulgaria