A CHARGE-CHARGE FLUX-OVERLAP INTERPRETATION OF THE INFRARED INTENSITIES OF HYDROGEN-BONDED SYSTEMS
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Date
1981
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Ohio State University
Abstract
The interpretation of infrared intensities using the concepts of atomic polar tensors divided according to contributions from charge-charge flux-overlap (CCFO) $terms^{2,3}$ appears to be quite useful in $general^{4}$ . Here we shall illustrate this analysis for the changes in infrared intensity for vibrations of the $H_{2}O$ molecule as it changes its environment from monomer to dimer. The important result is that only the charge flux contribution to the hydrogen-bonded H atom (and the corresponding contribution to the oxygen atoms) is predicted by ab initio calculations to change significantly from monomer to $dimer^{3}$. We shall discuss this result in terms of qualitative and more quantitative quantum-mechanical predictions of hydrogen-bond behaviour.
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$^{1}$J.F. Biarge, J. Herranz and J. Morcillo, An. R. Soc. Esp. Fis. Quim. Ser. A 57, 81 (1961); See also W.B. Person and J.H. Newton, J. Chem. Phys. 61, 1040 (1974). $^{2}$The concept of charge-charge flux contributions was introduced by J.C. Decius, J. Mol. Spectrosc. 57, 348 (1975) and modified and expanded to include overlap by W.T. King, in ``Vibrational Intensities'' (W.B. Person and G. Zerbi, Eds.) (Elsevier, Amsterdam, to be published 1981) Chapter 6. $^{3}$B. Zilles, Ph.D. thesis, University of Florida, 1980. $^{4}$For example see J. Rogers, Ph.D. thesis, University of Florida, 1980, and R. Maia, Ph.D thesis, University of Florida, 1980.
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