Effective Hamiltonian for Rotation-Inversion States of Ammonia-like Molecules

✍ Scribed by Kamil Sarka; Heinz W. Schrötter

• Publisher: Elsevier Science
• Year: 1996
• Tongue: English
• Weight: 246 KB
• Volume: 179
• Category: Article
• ISSN: 0022-2852
• DOI: 10.1006/jmsp.1996.0197

✦ Synopsis

A new effective correlation-free Hamiltonian is derived for the inversion-rotation states of ammonia-like molecules that is applicable to all isolated nondegenerate vibrational states including the ground vibrational state. Discrepancies between the existing theories and the applied fitting schemes are explained. It is shown that for the very large inversion splitting and for the negligible inversion splitting all nondiagonal terms connecting the inversion-rotation states can be removed by the appropriate reductions, whereas for the intermediate values of the inversion splitting the nondiagonal terms with the a constants cannot be removed. A clear physical meaning is given to the fitted parameters. The results are compared with the literature data.