Competition between charge migration and charge transfer induced by nuclear motion following core ionization: Model systems and application to Li<inf>2</inf><sup>+</sup>

Yang, L; Reimers, JR; Kobayashi, R; Hush, NS

Competition between charge migration and charge transfer induced by nuclear motion following core ionization: Model systems and application to Li<inf>2</inf><sup>+</sup>

Yang, L Reimers, JR

Kobayashi, R Hush, NS

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Publication Type:: Journal Article
Citation:: Journal of Chemical Physics, 2019, 151 (12)
Issue Date:: 2019-09-28

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Field	Value	Language
dc.contributor.author	Yang, L	en_US
dc.contributor.author	Reimers, JR https://orcid.org/0000-0001-5157-7422	en_US
dc.contributor.author	Kobayashi, R	en_US
dc.contributor.author	Hush, NS	en_US
dc.date.available	2020-09-30T19:08:21Z
dc.date.issued	2019-09-28	en_US
dc.identifier.citation	Journal of Chemical Physics, 2019, 151 (12)	en_US
dc.identifier.issn	0021-9606	en_US
dc.identifier.uri	http://hdl.handle.net/10453/136360
dc.description.abstract	© 2019 Author(s). Attosecond and femtosecond spectroscopies present opportunities for the control of chemical reaction dynamics and products, as well as for quantum information processing; we address the somewhat unique situation of core-ionization spectroscopy which, for dimeric chromophores, leads to strong valence charge localization and hence tightly paired potential-energy surfaces of very similar shape. Application is made to the quantum dynamics of core-ionized Li2+. This system is chosen as Li2 is the simplest stable molecule facilitating both core ionization and valence ionization. First, the quantum dynamics of some model surfaces are considered, with the surprising result that subtle differences in shape between core-ionization paired surfaces can lead to dramatic differences in the interplay between electronic charge migration and charge transfer induced by nuclear motion. Then, equation-of-motion coupled-cluster calculations are applied to determine potential-energy surfaces for 8 core-excited state pairs, calculations believed to be the first of their type for other than the lowest-energy core-ionized molecular pair. While known results for the lowest-energy pair suggest that Li2+ is unsuitable for studying charge migration, higher-energy pairs are predicted to yield results showing competition between charge migration and charge transfer. Central is a focus on the application of Hush's 1975 theory for core-ionized X-ray photoelectron spectroscopy to understand the shapes of the potential-energy surfaces and hence predict key features of charge migration.	en_US
dc.relation.ispartof	Journal of Chemical Physics	en_US
dc.relation.isbasedon	10.1063/1.5117246	en_US
dc.subject.classification	Chemical Physics	en_US
dc.title	Competition between charge migration and charge transfer induced by nuclear motion following core ionization: Model systems and application to Li<inf>2</inf><sup>+</sup>	en_US
dc.type	Journal Article
utslib.citation.volume	12	en_US
utslib.citation.volume	151	en_US
utslib.for	0203 Classical Physics	en_US
utslib.for	02 Physical Sciences	en_US
utslib.for	03 Chemical Sciences	en_US
utslib.for	09 Engineering	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.issue	12	en_US
pubs.publication-status	Published	en_US
pubs.volume	151	en_US

Abstract:

© 2019 Author(s). Attosecond and femtosecond spectroscopies present opportunities for the control of chemical reaction dynamics and products, as well as for quantum information processing; we address the somewhat unique situation of core-ionization spectroscopy which, for dimeric chromophores, leads to strong valence charge localization and hence tightly paired potential-energy surfaces of very similar shape. Application is made to the quantum dynamics of core-ionized Li2+. This system is chosen as Li2 is the simplest stable molecule facilitating both core ionization and valence ionization. First, the quantum dynamics of some model surfaces are considered, with the surprising result that subtle differences in shape between core-ionization paired surfaces can lead to dramatic differences in the interplay between electronic charge migration and charge transfer induced by nuclear motion. Then, equation-of-motion coupled-cluster calculations are applied to determine potential-energy surfaces for 8 core-excited state pairs, calculations believed to be the first of their type for other than the lowest-energy core-ionized molecular pair. While known results for the lowest-energy pair suggest that Li2+ is unsuitable for studying charge migration, higher-energy pairs are predicted to yield results showing competition between charge migration and charge transfer. Central is a focus on the application of Hush's 1975 theory for core-ionized X-ray photoelectron spectroscopy to understand the shapes of the potential-energy surfaces and hence predict key features of charge migration.

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http://hdl.handle.net/10453/136360