Dynamical hydrogen atom tunneling in dichlorotropolone: A combined quantum, semiclassical, and classical study
| Autor: | Hiroshi Ushiyama, Kazuo Takatsuka, Oliver Kühn, Kai Giese |
|---|---|
| Přispěvatelé: | Freie Universität Berlin |
| Jazyk: | angličtina |
| Rok vydání: | 2005 |
| Předmět: |
[PHYS]Physics [physics]
010304 chemical physics Chemistry Anharmonicity General Physics and Astronomy Semiclassical physics Hydrogen atom 01 natural sciences Correlation function MCTDH Quantum mechanics Saddle point 0103 physical sciences [CHIM]Chemical Sciences Configuration space Physical and Theoretical Chemistry 010306 general physics Wave function Quantum |
| Zdroj: | Journal of Chemical Physics Journal of Chemical Physics, American Institute of Physics, 2005, 122 (12), pp.124307. ⟨10.1063/1.1861888⟩ ResearcherID |
| ISSN: | 0021-9606 1089-7690 |
| Popis: | International audience; Based on the Cartesian Reaction Surface framework we construct a four-dimensional potential for the tropolone derivative 3,7-dichlorotropolone, a molecule with an intramolecular O-H...O hydrogen bond. The reduced configuration space involves the in-plane hydrogen atom coordinates, a symmetric O-O vibrational mode, and an antisymmetric mode related to deformations of the seven-membered ring. The system is characterized in terms of quantum mechanical computations of the low-lying eigenstates as well as a classical and semiclassical analysis of spectra obtained via Fourier transforming autocorrelation functions. For the semiclassical analysis we utilize the amplitude-free correlation function method [K. Hotta and K. Takatsuka, J. Phys. A 36, 4785 (2003)]. Our results demonstrate substantial anharmonic couplings leading to highly correlated wave functions even at moderate energies. Furthermore, the importance of dynamical tunneling in tropolone is suggested since many low-lying states--including the ground state--lie above the classical saddle point but nevertheless appear as split pairs. |
| Databáze: | OpenAIRE |
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