Nonadiabatic transition state theory: Application to intersystem crossings in the active sites of metal-sulfur proteins

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, intersystem crossing, metal-sulfur proteins, nonadiabatic transition state theory, 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-forbidden reactions, 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.

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Издание

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

Авторы

  • Lykhin Aleksandr O. (Univ Nevada, Dept Chem, Reno, NV 89557 USA; Siberian Fed Univ, Dept Chem, Krasnoyarsk 660041, Krasnoyarsk Kra, Russia)
  • Kaliakin Danil S. (Univ Nevada, Dept Chem, Reno, NV 89557 USA)
  • depolo Gwen E. (Univ Nevada, Dept Chem, Reno, NV 89557 USA)
  • Kuzubov Alexander A. (Siberian Fed Univ, Dept Chem, Krasnoyarsk 660041, Krasnoyarsk Kra, Russia)
  • Varganov Sergey A. (Univ Nevada, Dept Chem, Reno, NV 89557 USA)

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