Quantum chemical construction of a reduced reaction Hamiltonian and T
1
-relaxation and pure T
2
-dephasing rates for the proton transfer in 3-chlorotropolone |
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Authors: | R Xu YJ Yan O Kühn |
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Institution: | Open Laboratory of Bond-Selective Chemistry, University of Science and Technology of China, Hefei, China and Department of Chemistry, Hong Kong University of Science and Technology, Kowloon, Hong Kong SAR, P.R. China, HK Institut für Chemie, Physikalische und Theoretische Chemie, Freie Universit?t Berlin, Takustrasse 3, 14195 Berlin, Germany, DE
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Abstract: | Separating multidimensional problems into that of a relevant system which is coupled to a bath of harmonic oscillators is
a common concept in condensed phase theory. Focusing on the specific problem of intramolecular proton transfer in an isolated
tropolone derivative, we consider the reactive proton moving in the plane of the molecule as the system and the remaining
substrate normal modes as the bath. An all-Cartesian system-plus-substrate Hamiltonian is constructed employing density functional
theory. It is then used to determine the temperature-dependent effective reduced reaction Hamiltonian and the state-to-state
dissipation rates induced via the system-substrate coupling up to the bi-quadratic order. The important substrate modes for the T1-relaxation and the pure T2-dephasing rates, which are either intra- or inter-well in nature, are identified numerically and analyzed physically with
molecular details.
Received 19 November 2001 and Received in final form 19 February 2002 |
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Keywords: | PACS 31 70 Hq Time-dependent phenomena: excitation and relaxation processes and reaction rates – 82 30 Qt Isomerization and rearrangement – 31 15 Ar Ab initio calculations |
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