An investigation of one- versus two-dimensional semiclassical transition state theory for H atom abstraction and exchange reactions

Journal article

We investigate which terms in Reduced-Dimensionality Semiclassical Transition State Theory (RD SCTST) contribute most significantly in rate constant calculations of hydrogen extraction and exchange reactions of hydrocarbons. We also investigate the importance of deep tunneling corrections to the theory. In addition, we introduce a novel formulation of the theory in Jacobi coordinates. For the reactions of H atoms with methane, ethane, and cyclopropane, we find that a one-dimensional (1-D) version of the theory without deep tunneling corrections compares well with 2-D SCTST results and accurate quantum scattering results. For the "heavy-light-heavy" H atom exchange reaction between CH3 and CH4, deep tunneling corrections are needed to yield 1-D results that compare well with 2-D results. The finding that accurate rate constants can be obtained from derivatives of the potential along only one dimension further validates RD SCTST as a computationally efficient yet accurate rate constant theory.

Authors: Greene, S; Shan, X; Clary, D

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: AIP Publishing
• Journal: Journal of Chemical Physics
• Volume: 144
• Issue: 8
• Publication date: 2016-02-25
• Acceptance date: 2016-02-01
• DOI: 10.1063/1.4942161
• ISSN: 1089-7690 and 0021-9606
• Pmid: 26931687
• Language: English
• Keywords: SBTMR