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Quantum simulations of vibrational dephasing of molecules in a cryogenic environment: HArF in an argon cluster
Author(s) -
Jungwirth Pavel,
Gerber R. Benny,
Ratner Mark A.
Publication year - 2003
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1560/b2r2-bmua-am1l-hcmb
Subject(s) - dephasing , chemistry , excited state , relaxation (psychology) , argon , vibrational energy relaxation , excitation , quantum , atomic physics , cluster (spacecraft) , molecular dynamics , molecule , range (aeronautics) , molecular physics , chemical physics , computational chemistry , quantum mechanics , physics , psychology , social psychology , organic chemistry , computer science , programming language , materials science , composite material
The Classical Separable Potential (CSP) method, which is a meanfield approximation to multidimensional quantum dynamics, is applied to the dephasing process of a vibrationally excited HArF molecule in an argon cluster at low temperatures. Dephasing timescales of the order of 1 ps are estimated for dynamics following fundamental excitation of either the H–Ar or the Ar–F stretching mode of HArF. The CSP approach is valid over such timescales, and it is thus a viable approach to quantum simulations of dephasing at low temperatures. Vibrational relaxation is much slower: Quasi‐classical molecular dynamics simulations yield a relaxation time around 100 ps for the initial v = 1 Ar–F stretching excitation. Such timescales are beyond the validity range of CSP; therefore, this or similar separable methods are inapplicable for vibrational energy decay.