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Chemical reactions in the gas phase and in condensed matter: From wavefunctions to density operators
Author(s) -
Micha David A.
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22212
Subject(s) - wave function , chemistry , phase space , density matrix , operator (biology) , excited state , quantum , quantum mechanics , chemical reaction , statistical physics , physics , biochemistry , repressor , transcription factor , gene
Abstract This contribution generalizes the treatment of chemical reactions in the gas phase based on the reaction channel decomposition of the wavefunction, by introducing a similar channel decomposition of the statistical density operator valid also for condensed phases such as liquid solutions and solid surfaces. Coupled equations for the channel components of the density operator are derived and a brief presentation is given of their partial Wigner transform, which leads to a general treatment for coupling quantum and classical variables. This provides a general approach for reactions involving electronically excited states in many‐atom systems. It is pointed out that reactions involving coupled quantal and classical variables can be correctly described provided (a) initial conditions for trajectories are generated from quantal distributions and (b) the bundle of trajectories for the whole initial classical phase space is propagated coupled to the quantal elements of the density matrix and used in the calculation of reaction flux averages. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009