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• W2055496494 startingPage "4559" @default.
• W2055496494 abstract "A theory of the vibrational energy relaxation of a symmetric top molecule trapped in a rare gas matrix is presented. The direct relaxation mechanisms of the energy on the molecular orientation and on the lattice vibrations (including the local modes) are described within the framework of the nonadiabatic coupling between the internal vibrational mode of the molecule and the low-frequency external modes. The three types of relaxation constants are analyzed. The transfer to the orientational modes of the molecule is shown to be the more efficient since the corresponding relaxation time ranges between 1 μs and 50 ns, according to the nature of the rare gas matrix and to the temperature. The multiphonon relaxation constant is calculated for two specific deexcitation channels. The phonon multimode process provides relaxation times which range between 1 ms and 10 μs. Such a process is a characteristic of the nonadiabatic treatment of the total Hamiltonian. In contrast, the multiphonon monomode process, where the vibrational energy is transferred to the vibration of the center of mass of the molecule, gives larger relaxation times around 1 ms. This process is connected to the high orders in the interaction potential anharmonicity. The third species of relaxation constant which mix the orientational and translational processes is also analyzed for various typical relaxation channels. The corresponding relaxation times are one order of magnitude longer than those obtained from the multiphonon mechanisms. The calculated relaxation times are close to the experimental measurements and exhibit the same trends with rare gas changes and temperature rises." @default.
• W2055496494 created "2016-06-24" @default.
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• W2055496494 date "1987-10-15" @default.
• W2055496494 modified "2023-10-18" @default.
• W2055496494 title "Vibrational relaxation of ammonia trapped in rare gas matrices" @default.
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• W2055496494 doi "https://doi.org/10.1063/1.452868" @default.
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