Relating transition-state spectroscopy to standard chemical spectroscopic processes

Reimers, JR; Hush, NS

Relating transition-state spectroscopy to standard chemical spectroscopic processes

Reimers, JR

Hush, NS

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Publication Type:: Journal Article
Citation:: Chemical Physics Letters, 2017, 683 pp. 467 - 477
Issue Date:: 2017-09-01

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Field	Value	Language
dc.contributor.author	Reimers, JR https://orcid.org/0000-0001-5157-7422	en_US
dc.contributor.author	Hush, NS	en_US
dc.date.available	2020-05-25T19:01:57Z
dc.date.issued	2017-09-01	en_US
dc.identifier.citation	Chemical Physics Letters, 2017, 683 pp. 467 - 477	en_US
dc.identifier.issn	0009-2614	en_US
dc.identifier.uri	http://hdl.handle.net/10453/125251
dc.description.abstract	© 2017 Elsevier B.V. Transition-state spectra are mapped out using generalized adiabatic electron-transfer theory. This simple model depicts diverse chemical properties, from aromaticity, through bound reactions such as isomerizations and atom-transfer processes with classic transition states, to processes often described as being “non-adiabatic”, to those in the “inverted” region that become slower as they are made more exothermic. Predictably, the Born-Oppenheimer approximation is found inadequate for modelling transition-state spectra in the weak-coupling limit. In this limit, the adiabatic Born-Huang approximation is found to perform much better than non-adiabatic surface-hopping approaches. Transition-state spectroscopy is shown to involve significant quantum entanglement between electronic and nuclear motion.	en_US
dc.relation.ispartof	Chemical Physics Letters	en_US
dc.relation.isbasedon	10.1016/j.cplett.2017.04.070	en_US
dc.subject.classification	Chemical Physics	en_US
dc.title	Relating transition-state spectroscopy to standard chemical spectroscopic processes	en_US
dc.type	Journal Article
utslib.citation.volume	683	en_US
utslib.for	0202 Atomic, Molecular, Nuclear, Particle and Plasma Physics	en_US
utslib.for	0301 Analytical Chemistry	en_US
utslib.for	1003 Industrial Biotechnology	en_US
utslib.for	02 Physical Sciences	en_US
utslib.for	03 Chemical Sciences	en_US
utslib.for	10 Technology	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
utslib.copyright.status	open_access
pubs.publication-status	Published	en_US
pubs.volume	683	en_US

Abstract:

© 2017 Elsevier B.V. Transition-state spectra are mapped out using generalized adiabatic electron-transfer theory. This simple model depicts diverse chemical properties, from aromaticity, through bound reactions such as isomerizations and atom-transfer processes with classic transition states, to processes often described as being “non-adiabatic”, to those in the “inverted” region that become slower as they are made more exothermic. Predictably, the Born-Oppenheimer approximation is found inadequate for modelling transition-state spectra in the weak-coupling limit. In this limit, the adiabatic Born-Huang approximation is found to perform much better than non-adiabatic surface-hopping approaches. Transition-state spectroscopy is shown to involve significant quantum entanglement between electronic and nuclear motion.

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http://hdl.handle.net/10453/125251