Tunnelling in cyclocarbenes: An application of Semiclassical Transition State Theory in reduced dimensions

[Display omitted] •A hydrogen transfer reaction in cyclobutylidene is studied.•SCTST agrees well with previous VTST rate calculations, even at low temperature.•A framework for performing rate calculations in reduced dimensions is described.•2D-SCTST performs excellently despite significant savings c...

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Bibliographic Details
Published in:Chemical physics letters 2019-11, Vol.735, p.136783, Article 136783
Main Authors: Burd, Timothy A.H., Shan, Xiao, Clary, David C.
Format: Article
Language:English
Subjects:
Carbene
Semiclassical Transition State Theory
Tunnelling
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Summary:[Display omitted] •A hydrogen transfer reaction in cyclobutylidene is studied.•SCTST agrees well with previous VTST rate calculations, even at low temperature.•A framework for performing rate calculations in reduced dimensions is described.•2D-SCTST performs excellently despite significant savings compared to full-dimensions. Methods to calculate rates of chemical reactions ab initio, in reduced dimensions, using Semiclassical Transition State Theory have recently been formulated. Here we further develop its application to unimolecular reactions where the choice of active degrees of freedom is not clear a priori. We describe in more detail a procedure to determine which degrees of freedom must be accounted for explicitly in the reduced dimensionality framework, and illustrate its success on a hydrogen transfer reaction of a cyclocarbene species.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2019.136783