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Analytic evaluation of nonadiabatic couplings within the complex absorbing potential equation-of-motion coupled-cluster method
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Chatterjee, Koushik, Koczor-Benda, Zsuzsanna, Feng, Xintian, Krylov, Anna I. and Jagau, Thomas-C. (2023) Analytic evaluation of nonadiabatic couplings within the complex absorbing potential equation-of-motion coupled-cluster method. Journal of Chemical Theory and Computation, 19 (17). pp. 5821-5834. doi:10.1021/acs.jctc.3c00514 ISSN 1549-9618.
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Official URL: https://doi.org/10.1021/acs.jctc.3c00514
Abstract
We present the theory for the evaluation of nonadiabatic couplings (NACs) involving resonance states within the complex absorbing potential equation-of-motion coupled-cluster (CAP-EOM-CC) framework implemented within the singles and doubles approximation. Resonance states are embedded in the continuum and undergo rapid decay through autodetachment. In addition, nuclear motion can facilitate transitions between different resonances and between resonances and bound states. These nonadiabatic transitions affect the chemical fate of resonances and have distinct spectroscopic signatures. The NAC vector is a central quantity needed to model such effects. In the CAP-EOM-CC framework, resonance states are treated on the same footing as bound states. Using the example of fumaronitrile, which supports a bound radical anion and several anionic resonances, we analyze the NAC between bound states and pseudocontinuum states, between bound states and resonances, and between two resonances. We find that the NAC between a bound state and a resonance is nearly independent of the CAP strength and thus straightforward to evaluate, whereas the NAC between two resonance states or between a bound state and a pseudocontinuum state is more difficult to evaluate.
Item Type: | Journal Article | ||||||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||
SWORD Depositor: | Library Publications Router | ||||||||||||
Library of Congress Subject Headings (LCSH): | Anions, Chemical bonds, Mesomerism | ||||||||||||
Journal or Publication Title: | Journal of Chemical Theory and Computation | ||||||||||||
Publisher: | American Chemical Society | ||||||||||||
ISSN: | 1549-9618 | ||||||||||||
Official Date: | 12 September 2023 | ||||||||||||
Dates: |
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Volume: | 19 | ||||||||||||
Number: | 17 | ||||||||||||
Page Range: | pp. 5821-5834 | ||||||||||||
DOI: | 10.1021/acs.jctc.3c00514 | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Re-use Statement: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jctc.3c00514 | ||||||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||||||
Date of first compliant deposit: | 22 November 2023 | ||||||||||||
RIOXX Funder/Project Grant: |
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Open Access Version: |
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