Modeling the Kinetics of Bimolecular Reactions

@article{Fernandez-Ramos:2006, abstract = {This review is concerned with the theoretical and computational modeling of bimolecular reactions, especially with generally applicable methods for kinetics (i.e., overall rates as opposed to detailed dynamics). It includes a basic theoretical framework that can be used for gas-phase thermal reactions, gas-phase microcanonical and state-selected reactions, and condensed-phase chemical reactions. The treatment of gas-phase thermal reactions includes separate discussions of simple direct reactions over a barrier, which usually have tight transition states and reactions proceeding over a chemical potential well, which can have a number of additional complications, such as barrierless addition potentials (which generally have loose, flexible transition states), competitive reaction pathways, isomerizations between multiple wells, and pressure-dependent energy transfer processes. The section on thermal reactions has a heavy emphasis on (generalized) transition state theory (TST) including multidimensional tunneling because this theory provides the best available method to calculate thermal rate constants for all but the very simplest systems. The section on state-selective reactions and product state distributions includes an introduction to the theory of electronically nonadiabatic reactions and coupled potential energy surfaces, as required for modeling photochemical and chemiluminescent reactions. The section on bimolecular reactions in liquid solution considers diffusion control and equilibrium and nonequilibrium solvation.}, annote = {Modeling the Kinetics of Bimolecular Reactions}, author = {Ramos, Fernandez A. and Miller, J. A. and Klippenstein, S. J. and Truhlar, D. G. }, citeulike-article-id = {1331653}, journal = {Chemical Reviews}, keywords = {diffusion}, number = {11}, pages = {4518--84}, posted-at = {2007-05-25 14:24:57}, priority = {0}, title = {Modeling the Kinetics of Bimolecular Reactions}, url = {http://dx.doi.org/10.1021/cr050205w}, volume = {106}, year = {2006} }

TY - JOUR ID - Fernandez-Ramos:2006 L3 - citeulike-article-id:1331653 TI - Modeling the Kinetics of Bimolecular Reactions JF - Chemical Reviews VL - 106 IS - 11 SP - 4518 EP - 84 N2 - This review is concerned with the theoretical and computational modeling of bimolecular reactions, especially with generally applicable methods for kinetics (i.e., overall rates as opposed to detailed dynamics). It includes a basic theoretical framework that can be used for gas-phase thermal reactions, gas-phase microcanonical and state-selected reactions, and condensed-phase chemical reactions. The treatment of gas-phase thermal reactions includes separate discussions of simple direct reactions over a barrier, which usually have tight transition states and reactions proceeding over a chemical potential well, which can have a number of additional complications, such as barrierless addition potentials (which generally have loose, flexible transition states), competitive reaction pathways, isomerizations between multiple wells, and pressure-dependent energy transfer processes. The section on thermal reactions has a heavy emphasis on (generalized) transition state theory (TST) including multidimensional tunneling because this theory provides the best available method to calculate thermal rate constants for all but the very simplest systems. The section on state-selective reactions and product state distributions includes an introduction to the theory of electronically nonadiabatic reactions and coupled potential energy surfaces, as required for modeling photochemical and chemiluminescent reactions. The section on bimolecular reactions in liquid solution considers diffusion control and equilibrium and nonequilibrium solvation. KW - diffusion AU - Ramos, Fernandez AU - Miller, JA AU - Klippenstein, SJ AU - Truhlar, DG PY - 2006/// UR - http://dx.doi.org/10.1021/cr050205w ER -