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Hydrogen tunnelling in the rearrangements of carbenes: the role of dynamical calculations

Abstract:
Tunnelling controlled chemical reactions are those which preferably proceed through pathways with high but narrow potential energy barriers, via quantum tunnelling, resulting in a product that would be disfavoured classically. These reactions are very sensitive to barrier width, height and temperature and so dynamical theoretical methods are required to describe these processes. Recent experimental work on charge-tagged phenyl pyruvic acid derivatives has found, in contrast to similar systems, no evidence of tunnelling control. Using semiclassical transition state theory, we rationalise these results and find tunnelling is significant in this system.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1039/c9cp06300e

Authors

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Physical & Theoretical Chem
Role:
Author
ORCID:
0000-0002-7331-8007
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Physical & Theoretical Chem
Role:
Author
ORCID:
0000-0003-1603-0338
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Physical & Theoretical Chem
Oxford college:
Magdalen College
Role:
Author
ORCID:
0000-0003-4439-741X


Publisher:
Royal Society of Chemistry
Journal:
Physical Chemistry Chemical Physics More from this journal
Volume:
22
Issue:
3
Pages:
962-965
Publication date:
2019-12-17
Acceptance date:
2019-12-17
DOI:
EISSN:
1463-9084
ISSN:
1463-9076
Pmid:
31872828


Language:
English
Keywords:
Pubs id:
1079718
Local pid:
pubs:1079718
Deposit date:
2020-02-21
ARK identifier:

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