Semiclassical Transition State Theory (SCTST) is an efficient chemical rate theory, which aims to calculate accurate rate constants of chemical reactions, including nuclear quantum effects such as tunnelling, from ab initio quantum chemistry. The method makes use of the semiclassical WKB wavefunction, Bohr-sommerfeld theory and vibrational perturbation 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 by Bill Miller and coworkers in the 1970's, and has been further developed to allow for application to larger systems and using more accurate potentials.
References
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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. ISSN 0009-2614. /wiki/Bibcode_(identifier) ↩
Greene, Samuel M.; Shan, Xiao; Clary, David C. (2016-02-28). "An investigation of one- versus two-dimensional semiclassical transition state theory for H atom abstraction and exchange reactions". The Journal of Chemical Physics. 144 (8): 084113. Bibcode:2016JChPh.144h4113G. doi:10.1063/1.4942161. PMID 26931687. https://ora.ox.ac.uk/objects/uuid:f40d1c11-38c2-470c-9875-27088663125b ↩
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. ISBN 978-981-314-734-8. 978-981-314-734-8 ↩
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. /wiki/Bibcode_(identifier) ↩
Barker, John R.; Stanton, John F.; Nguyen, Thanh Lam (2010-10-20). "A practical implementation of semi-classical transition state theory for polyatomics". Chemical Physics Letters. 499 (1–3): 9–15. Bibcode:2010CPL...499....9N. doi:10.1016/j.cplett.2010.09.015. ISSN 0009-2614. https://utexas.influuent.utsystem.edu/en/publications/a-practical-implementation-of-semi-classical-transition-state-the ↩
Wagner, Albert F. (2013-11-26). "Improved Multidimensional Semiclassical Tunneling Theory". The Journal of Physical Chemistry A. 117 (49): 13089–13100. Bibcode:2013JPCA..11713089W. doi:10.1021/jp409720s. PMID 24224758. /wiki/Bibcode_(identifier) ↩