THE THEORY OF THE NON-RESONANT RAMAN EFFECT AND VIBRATIONAL CORRECTIONS TO SECOND-ORDER PROPERTIES

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1973

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Ohio State University

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The theory of Rayleigh and Raman intensities far from resonance has been reinvestigated. A closely related problem, the effect of nuclear motion on the optical second-order properties, has been considered as well. The correct simplification of the Kramers-Heisenberg dispersion equation is that proposed, though not justified, by Pleaczek, in which diagonal and transition matrix elements of the electric polarizability tensor are computed. Higher-order terms are formally shown here to be small and various correction terms leading to the exact dispersion equation, within the Born-Oppenheimer approximation, have been evaluated. Representative calculations on $H_{2}^{+}$, which is both exactly soluble and for which the parallel and perpendicular components represent highly and less polarizable molecules, respectively, are given for transitions between all bound vibrational states. A complete test of the approximate theory is thus made, including Herzberg-Teller expansions.

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Author Institution: City University of New York at Queens College

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