Chemistry:Nonadiabatic transition state theory
Nonadiabatic transition state theory (NA-TST) is a powerful tool to predict rates of chemical reactions from a computational standpoint. NA-TST has been introduced in 1988 by Prof. J.C. Lorquet.[1] In general, all of the assumptions taking place in traditional transition state theory (TST) are also used in NA-TST but with some corrections. First, a spin-forbidden reaction proceeds through the minimum energy crossing point (MECP) rather than through transition state (TS).[2] Second, unlike TST, the probability of transition is not equal to unity during the reaction and treated as a function of internal energy associated with the reaction coordinate.[3] At this stage non-relativistic couplings responsible for mixing between states is a driving force of transition. For example, the larger spin-orbit coupling at MECP the larger the probability of transition. NA-TST can be reduced to the traditional TST in the limit of unit probability.[3]
References
- ↑ Lorquet, J. C.; Leyh-Nihant, B. (2002-05-01). "Nonadiabatic unimolecular reactions. 1. A statistical formulation for the rate constants" (in EN). The Journal of Physical Chemistry 92 (16): 4778–4783. doi:10.1021/j100327a043.
- ↑ Harvey, Jeremy N. (2007-01-02). "Understanding the kinetics of spin-forbidden chemical reactions" (in en). Phys. Chem. Chem. Phys. 9 (3): 331–343. doi:10.1039/b614390c. ISSN 1463-9084. PMID 17199148. Bibcode: 2007PCCP....9..331H. http://xlink.rsc.org/?DOI=B614390C.
- ↑ 3.0 3.1 Lykhin, Aleksandr O.; Kaliakin, Danil S.; dePolo, Gwen E.; Kuzubov, Alexander A.; Varganov, Sergey A. (2016-05-15). "Nonadiabatic transition state theory: Application to intersystem crossings in the active sites of metal-sulfur proteins" (in en). International Journal of Quantum Chemistry 116 (10): 750–761. doi:10.1002/qua.25124. ISSN 1097-461X.
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