An ab initio calculation of the intramolecular stretching spectra for the HF dimer and its D‐substituted isotopic species
| Autor: | Philip R. Bunker, Manfred Kofranek, Per Jensen, Hans Lischka, Alfred Karpfen |
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| Rok vydání: | 1990 |
| Předmět: |
Quantitative Biology::Biomolecules
Chemistry Transition dipole moment Ab initio General Physics and Astronomy Quantum number Diatomic molecule Molecular physics Dipole Ab initio quantum chemistry methods Computational chemistry Intramolecular force Kinetic isotope effect Physics::Chemical Physics Physical and Theoretical Chemistry |
| Zdroj: | The Journal of Chemical Physics. 93:6266-6280 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/1.458996 |
| Popis: | We have carried out an ab initio calculation of the intramolecular stretching spectra (wave numbers and transition moments) of (HF)2, (DF)2, and HFDF involving v1+v2≤3, where v1 and v2 are the local mode quantum numbers for the two intramolecular (HF or DF) stretches. The ab initio surface used as a basis for these calculations has already been published [M. Kofranek, H. Lischka, and A. Karpfen, Chem. Phys. 121, 137 (1988); P. R. Bunker, P. Jensen, A. Karpfen, M. Kofranek, and H. Lischka, J. Chem. Phys. 92, 7432 (1990)], but in the present work we have extended the 1520 nuclear geometry points previously available with 198 points in order to explore further the variation of the intramolecular stretching energies and the dipole moment along the minimum energy (trans tunneling) path. We compute the intramolecular stretching energies and transition moments by making an adiabatic separation of the intramolecular stretching motion and the other vibrational motions of the molecules, and we use the semirigid ben... |
| Databáze: | OpenAIRE |
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