True and effective polarizability tensors for asymmetric-top molecules: The rotational Raman spectra of H2S and D2S
| Autor: | W. F. Murphy, J.M. Fernández-Sánchez |
|---|---|
| Rok vydání: | 1992 |
| Předmět: |
Physics
Triatomic molecule Anharmonicity Rotational transition Molecular physics Atomic and Molecular Physics and Optics symbols.namesake Nuclear magnetic resonance Polarizability symbols Depolarization ratio Physical and Theoretical Chemistry Raman spectroscopy Anisotropy Spectroscopy Raman scattering |
| Zdroj: | Journal of Molecular Spectroscopy. 156:444-460 |
| ISSN: | 0022-2852 |
| Popis: | Higher order contributions to the rotational matrix elements of the equilibrium polarizability tensor are here derived from the components of the effective polarizability, obtained by contact transformation of the true polarizability tensor. These are used to simulate the rotational Raman spectrum of H 2 S. The J -dependent intensity contribution from the (first-order) centrifugal distortion term is needed to give a good comparison with the observed spectrum. The best calculated spectrum is that having an integrated intensity which is consistent with the polarizability anisotropy obtained from the earlier depolarization ratio measurement. The calculation serves to determine the relative signs of both the equilibrium polarizability components and the derivatives with respect to normal coordinates—only one sign combination yields a calculated spectrum which agrees with the observed one. The cubic anharmonicity term also makes a significant isotopedependent contribution to the J -independent terms. These values were then used to derive the effective polarizability components for D 2 S from the true ones, and they give a calculated spectrum and integrated intensity which agree well with observed results. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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