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Analytical gradients for core-excited states in the algebraic diagrammatic construction (ADC) framework
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology. Pohang Univ Sci & Technol POSTECH, Dept Chem, Pohang 37673, South Korea.ORCID iD: 0000-0003-1671-8298
Heidelberg Univ, Interdisciplinary Ctr Sci Comp, D-69120 Heidelberg, Germany..
Heidelberg Univ, Interdisciplinary Ctr Sci Comp, D-69120 Heidelberg, Germany..
Korea Adv Inst Sci & Technol, Dept Chem, Daejeon 34141, South Korea..ORCID iD: 0000-0002-2392-3962
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2021 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 155, no 4, article id 044106Article in journal (Refereed) Published
Abstract [en]

Expressions for analytical molecular gradients of core-excited states have been derived and implemented for the hierarchy of algebraic diagrammatic construction (ADC) methods up to extended second-order within the core-valence separation (CVS) approximation. We illustrate the use of CVS-ADC gradients by determining relaxed core-excited state potential energy surfaces and optimized geometries for water, formic acid, and benzene. For water, our results show that in the dissociative lowest core-excited state, a linear configuration is preferred. For formic acid, we find that the O K-edge lowest core-excited state is non-planar, a fact that is not captured by the equivalent core approximation where the core-excited atom with its hole is replaced by the "Z + 1" neighboring atom in the periodic table. For benzene, the core-excited state gradients are presented along the Jahn-Teller distorted geometry of the 1s -> pi* excited state. Our development may pave a new path to studying the dynamics of molecules in their core-excited states.

Place, publisher, year, edition, pages
AIP Publishing , 2021. Vol. 155, no 4, article id 044106
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-302001DOI: 10.1063/5.0058221ISI: 000692373900001PubMedID: 34340367Scopus ID: 2-s2.0-85111674108OAI: oai:DiVA.org:kth-302001DiVA, id: diva2:1594909
Note

QC 20210916

Available from: 2021-09-16 Created: 2021-09-16 Last updated: 2022-06-25Bibliographically approved

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Brumboiu, Iulia E.Norman, Patrick

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