Semiclassical Transition State Theory (SCTST)[1][2] is an efficient chemical rate theory, which aims to calculate accuraterate constants of chemical reactions, including nuclear quantum effects such astunnelling, from ab initioquantum chemistry.[3][4][5] The method makes use of the semiclassicalWKB wavefunction,Bohr-sommerfeld theory and vibrationalperturbation theory to derive an analytical relation for the probability of a particle transmitting through a potential barrier at some energy, E. It was first developed byBill Miller and coworkers in the 1970's, and has been further developed to allow for application to larger systems[6] and using more accurate potentials.[7]
^Miller, William H.; Hernandez, Rigoberto; Handy, Nicholas C.; Jayatilaka, Dylan; Willetts, Andrew (1990-08-24). "Ab initio calculation of anharmonic constants for a transition state, with application to semiclassical transition state tunneling probabilities".Chemical Physics Letters.172 (1):62–68.Bibcode:1990CPL...172...62M.doi:10.1016/0009-2614(90)87217-F.ISSN0009-2614.
^Nguyen, Thanh Lam; Barker, John R.; Stanton, John F. (2016-08-14). "Atmospheric Reaction Rate Constants and Kinetic Isotope Effects Computed Using the HEAT Protocol and Semi-Classical Transition State Theory".Advances in Atmospheric Chemistry.World Scientific. pp. 403–492.doi:10.1142/9789813147355_0006.ISBN978-981-314-734-8.
^Miller, William H. (1975). "Semiclassical limit of quantum mechanical transition state theory for nonseparable systems".The Journal of Chemical Physics.62 (5):1899–1906.Bibcode:1975JChPh..62.1899M.doi:10.1063/1.430676.
