Six-dimensional quantum calculations of vibration-rotation-tunneling levels of ν1 and ν2 HCl-stretching excited (HCl)2
| Autor: | Yanhui Qiu, John Z. H. Zhang, Zlatko Bačić |
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| Rok vydání: | 1998 |
| Předmět: | |
| Zdroj: | The Journal of Chemical Physics. 108:4804-4816 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/1.475891 |
| Popis: | Results of the first full-dimensional (6D) quantum calculations of the vibrational levels of the ν1 and ν2 HCl-stretch excited (HCl)2, for total angular momentum J=0, are presented. Three 6D potential energy surfaces (PESs) were employed. Two widely used PESs, the ab initio PES of Bunker and co-workers and the semiempirical PES by Elrod and Saykally, are found to give negligible tunneling splittings (⩽5×10−2 cm−1) for the vibrational eigenstates of the ν1/ν2 excited (HCl)2, in sharp disagreement with the experimental tunneling splittings in the ν1 and ν2 fundamentals, −3.32 and 3.18 cm−1. In an effort to overcome this problem, a 6D electrostatic interaction potential is constructed and added to the ES1 PES; the resulting 6D PES is denoted ES1-EL. Quantum 6D calculations on the ES1-EL PES yield greatly improved tunneling splittings for ν1 (−2.31 cm−1) and ν2 (2.45 cm−1), which are 70% and 77%, respectively, of the corresponding experimental values. The ν1 and ν2 fundamental HCl-stretching frequencies calcu... |
| Databáze: | OpenAIRE |
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