Formulas for the transition probabilities and hence the absolute intensities of molecular vibrational spectra are obtained from a unified quantum field treatment. The theory of infrared, Raman, and hyper‐Raman spectroscopy of molecular vibrations is developed by assuming these processes occur as time‐ordered steps involving the creation or destruction of one quantum of vibrational energy and changes in the occupation number of one, two, or three photons, respectively. The formulas obtained by this method for ir transitions become equivalent to the earlier treatment of Jones and Simpson if the energy difference of the ground and first excited electronic energy levels are very large relative to that of the vibrational quantum. The formulas obtained for Raman transitions are very similar to those obtained by the method originated by Albrecht and developed further by Savin; we get not only the original terms of Albrecht but also the trace terms obtained by Savin. Furthermore by using third‐order time‐dependent equations from the start we avoid many of the difficulties of the earlier treatments; our equations predict different conditions for the resonant Raman effect than do the earlier equations, and experiments are suggested for testing the new equations. The formula which we give for the absolute intensity of the hyper‐Raman effect appears to be the first ever given.
Skip Nav Destination
Article navigation
1 February 1970
Research Article|
February 01 1970
Quantum Theory of the Intensities of Molecular Vibrational Spectra Available to Purchase
Warner L. Peticolas;
Warner L. Peticolas
Department of Chemistry, University of Oregon, Eugene, Oregon 97403
Search for other works by this author on:
Laurence Nafie;
Laurence Nafie
Department of Chemistry, University of Oregon, Eugene, Oregon 97403
Search for other works by this author on:
Paul Stein;
Paul Stein
Department of Chemistry, University of Oregon, Eugene, Oregon 97403
Search for other works by this author on:
Bruno Fanconi
Bruno Fanconi
Department of Chemistry, University of Oregon, Eugene, Oregon 97403
Search for other works by this author on:
Warner L. Peticolas
Department of Chemistry, University of Oregon, Eugene, Oregon 97403
Laurence Nafie
Department of Chemistry, University of Oregon, Eugene, Oregon 97403
Paul Stein
Department of Chemistry, University of Oregon, Eugene, Oregon 97403
Bruno Fanconi
Department of Chemistry, University of Oregon, Eugene, Oregon 97403
J. Chem. Phys. 52, 1576–1584 (1970)
Article history
Received:
July 21 1969
Citation
Warner L. Peticolas, Laurence Nafie, Paul Stein, Bruno Fanconi; Quantum Theory of the Intensities of Molecular Vibrational Spectra. J. Chem. Phys. 1 February 1970; 52 (3): 1576–1584. https://doi.org/10.1063/1.1673170
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
Related Content
Analysis and prediction of absorption band shapes, fluorescence band shapes, resonance Raman intensities, and excitation profiles using the time-dependent theory of electronic spectroscopy
J. Chem. Phys. (October 2007)
Solvatochromic shifts of polar and non-polar molecules in ambient and supercritical water: A sequential quantum mechanics/molecular mechanics study including solute-solvent electron exchange-correlation
J. Chem. Phys. (December 2012)
Density matrix renormalization group with efficient dynamical electron correlation through range separation
J. Chem. Phys. (June 2015)
On the local representation of the electronic momentum operator in atomic systems
J. Chem. Phys. (July 2008)
A connection between domain-averaged Fermi hole orbitals and electron number distribution functions in real space
J. Chem. Phys. (September 2009)