Тип публикации: статья из журнала
Год издания: 2016
Идентификатор DOI: 10.1002/qua.25124
Ключевые слова: intersystem crossing, nonadiabatic transition state theory, metal-sulfur proteins, Computation theory, Electronic states, Proteins, Sulfur, Inter-system crossings, Large complex systems, Non-adiabatic transitions, Non-radiative transitions, Partition functions, Transition probabilities, Transition state theories, [NiFe]-hydrogenase, Rate constants
Аннотация: Nonadiabatic transition state theory (NA-TST) is a powerful tool to investigate the nonradiative transitions between electronic states with different spin multiplicities. The statistical nature of NA-TST provides an elegant and computationally inexpensive way to calculate the rate constants for intersystem crossings, spin-forbiddenПоказать полностьюreactions, and spin-crossovers in large complex systems. The relations between the microcanonical and canonical versions of NA-TST and the traditional transition state theory are shown, followed by a review of the basic steps in a typical NA-TST rate constant calculation. These steps include evaluations of the transition probability and coupling between electronic states with different spin multiplicities, a search for the minimum energy crossing point (MECP), and computing the densities of states and partition functions for the reactant and MECP structures. The shortcomings of the spin-diabatic version of NA-TST related to ill-defined state coupling and state counting are highlighted. In three examples, we demonstrate the application of NA-TST to intersystem crossings in the active sites of metal-sulfur proteins focusing on [NiFe]-hydrogenase, rubredoxin, and Fe2S2-ferredoxin. (c) 2016 Wiley Periodicals, Inc.
Журнал: INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
Выпуск журнала: Vol. 116, Is. 10
Номера страниц: 750-761
ISSN журнала: 00207608
Место издания: HOBOKEN
Издатель: WILEY-BLACKWELL