A vibrational CASSCF study of stretch-bend interactions and their influence on infrared intensities in the water molecule |
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Authors: | F. Culot F. Laruelle J. Liévin |
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Affiliation: | (1) Laboratoire de Chimie Physique Moléculaire, Université Libre de Bruxelles, Ave. F.D. Roosevelt, CP. 160/09, B-1050 Bruxelles, Belgium |
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Abstract: | Summary An extension of the multiconfigurational SCF approach for the resolution of the vibrational problem is presented; it follows the philosophy of the CASSCF method developed in Quantum Chemistry. The new method allows a more complete treatment of anharmonic mode couplings, converges much faster and gives a clearer physical insight of vibrational interactions. This is exemplified by the calculation of infrared transition moments in the H2O and D2O isotopomers of the water molecule. It is shown how this property varies with the quality of the wave function when vibrational resonances occur. A detailed analysis by means of this new VCASSCF method demonstrates the crucial importance of excited bending oscillators in the intensity of some pure stretching transitions.Boursier F.R.I.A. |
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Keywords: | Vibrational structure calculations Anharmonic couplings Vibrational resonances Infrared intensities Multiconfigurational methods |
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