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A dynamic mean field theory for dissipative interacting many‐electron systems: Markovian formalism and its implementation
Author(s) -
Yokojima Satoshi,
Chen Guanhua,
Xu Ruixue,
Yan Yijing
Publication year - 2003
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10370
Subject(s) - dissipative system , excitation , electron , physics , markov process , formalism (music) , statistical physics , quantum mechanics , quantum , phonon , valence (chemistry) , atomic physics , mathematics , art , musical , statistics , visual arts
To demonstrate its applicability for realistic open systems, we apply the dynamic mean field quantum dissipative theory to simulate the photo‐induced excitation and nonradiative decay of an embedded butadiene molecule. The Markovian approximation is adopted to further reduce the computational time, and the resulting Markovian formulation assumes a variation of Lindblad's semigroup form, which is shown to be numerically stable. In the calculation, all 22 valence electrons in the butadiene molecule are taken as the system and treated explicitly while the nuclei of the molecules are taken as the immediate bath of the system. It is observed that (1) various excitations decay differently, which leads to different peak widths in the absorption spectra; and (2) the temperature dependences of nonradiative decay rates are distinct for various excitations, which can be explained by the different electron‐phonon couplings. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 2083–2092, 2003