Journal
FARADAY DISCUSSIONS
Volume 157, Issue -, Pages 59-88Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2fd20012k
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Funding
- U.S. Department of Energy, Office of Basic Energy Sciences [DE-FG02-86ER13579]
- Combustion Energy Frontier Research Center [DE-SC0001198]
- U.S. Department of Energy's Office of Biological and Environmental Research
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Complex molecules often have many structures (conformations) of the reactants and the transition states, and these structures may be connected by coupled-mode torsions and pseudorotations; some but not all structures may have hydrogen bonds in the transition state or reagents. A quantitative theory of the reaction rates of complex molecules must take account of these structures, their coupled-mode nature, their qualitatively different character, and the possibility of merging reaction paths at high temperature. We have recently developed a coupled-mode theory called multi-structural variational transition state theory (MS-VTST) and an extension, called multi-path variational transition state theory (MP-VTST), that includes a treatment of the differences in the multidimensional tunneling paths and their contributions to the reaction rate. The MP-VTST method was presented for unimolecular reactions in the original paper and has now been extended to bimolecular reactions. The MS-VTST and MP-VTST formulations of variational transition state theory include multi-faceted configuration-space dividing surfaces to define the variational transition state. They occupy an intermediate position between single-conformation variational transition state theory (VTST), which has been used successfully for small molecules, and ensemble-averaged variational transition state theory (EA-VTST), which has been used successfully for enzyme kinetics. The theories are illustrated and compared here by application to three thermal rate constants for reactions of ethanol with hydroxyl radical-reactions with 4, 6, and 14 saddle points.
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