Chemistry:Semiclassical transition state theory

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Short description: Chemical reaction rate theory

Semiclassical Transition State Theory (SCTST)[1][2] 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.[3][4][5] 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[6] and using more accurate potentials.[7]

References

  1. ↑ Burd, Timothy A.H.; Shan, Xiao; Clary, David C. (2018-02-01). "Tunnelling and the kinetic isotope effect in CH3+CH4→CH4+CH3: An application of semiclassical transition state theory" (in en). Chemical Physics Letters 693: 88–94. doi:10.1016/j.cplett.2018.01.002. ISSN 0009-2614. https://ora.ox.ac.uk/objects/uuid:500ef046-8ad9-43b6-9b49-47cd320d4a71. 
  2. ↑ 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" (in en). Chemical Physics Letters 172 (1): 62–68. doi:10.1016/0009-2614(90)87217-F. ISSN 0009-2614. 
  3. ↑ 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" (in en-us). The Journal of Chemical Physics 144 (8): 084113. doi:10.1063/1.4942161. PMID 26931687. https://ora.ox.ac.uk/objects/uuid:f40d1c11-38c2-470c-9875-27088663125b. 
  4. ↑ 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" (in en-us). Advances in Atmospheric Chemistry. Advances in Atmospheric Chemistry. World Scientific. pp. 403–492. doi:10.1142/9789813147355_0006. ISBN 978-981-314-734-8. 
  5. ↑ Miller, William H. (1975). "Semiclassical limit of quantum mechanical transition state theory for nonseparable systems". The Journal of Chemical Physics 62 (5): 1899–1906. doi:10.1063/1.430676. 
  6. ↑ 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. 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. 
  7. ↑ Wagner, Albert F. (2013-11-26). "Improved Multidimensional Semiclassical Tunneling Theory" (in EN). The Journal of Physical Chemistry A 117 (49): 13089–13100. doi:10.1021/jp409720s. PMID 24224758. 



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