Transmission Coefficients for Chemical Reactions with Multiple States: Role of Quantum Decoherence

0367724 - ÚOCHB 2012 RIV US eng J - Journal Article
de la Lande, A. - Řezáč, Jan - Lévy, B. - Sanders, B. C. - Salahub, D. R.
Transmission Coefficients for Chemical Reactions with Multiple States: Role of Quantum Decoherence.
Journal of the American Chemical Society. Roč. 133, č. 11 (2011), s. 3883-3894. ISSN 0002-7863. E-ISSN 1520-5126
Institutional research plan: CEZ:AV0Z40550506
Keywords : decoherence * transition state theory * nonadiabatic reactions
Subject RIV: CC - Organic Chemistry
Impact factor: 9.907, year: 2011

A simple modification to the usual TST rate constant expression is proposed: in addition to the electronic coupling, a characteristic decoherence time τdec now also appears as a key parameter of the rate constant. This new parameter captures the idea that molecular systems, although intrinsically obeying quantum mechanical laws, behave semiclassically after a finite but nonzero amount of time (dec). This new degree of freedom allows a fresh look at the underlying physics of chemical reactions involving more than one quantum state. The ability of the proposed formula to describe the main physical lines of the phenomenon is confirmed by comparison with results obtained from density functional theory molecular dynamics simulations for a triplet to singlet transition within a copper dioxygen adduct relevant to the question of dioxygen activation by copper monooxygenases.
Permanent Link: http://hdl.handle.net/11104/0202296