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Efficient calculations of a large number of highly excited states for multiconfigurational wavefunctions
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0001-9883-3569
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0001-9418-6579
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0003-4020-0923
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2019 (English)In: Journal of Computational Chemistry, ISSN 0192-8651, E-ISSN 1096-987X, Vol. 40, no 19, p. 1789-1799Article in journal (Refereed) Published
Abstract [en]

Electronically excited states play important roles in many chemical reactions and spectroscopic techniques. In quantum chemistry, a common technique to solve excited states is the multiroot Davidson algorithm, but it is not designed for processes like X-ray spectroscopy that involves hundreds of highly excited states. We show how the use of a restricted active space wavefunction together with a projection operator to remove low-lying electronic states offers an efficient way to reach single and double-core-hole states. Additionally, several improvements to the stability and efficiency of the configuration interaction (CI) algorithm for a large number of states are suggested. When applied to a series of transition metal complexes the new CI algorithm does not only resolve divergence issues but also leads to typical reduction in computational time by 70%, with the largest savings for small molecules and large active spaces. Together, the projection operator and the improved CI algorithm now make it possible to simulate a wide range of single- and two-photon spectroscopies.

Place, publisher, year, edition, pages
WILEY , 2019. Vol. 40, no 19, p. 1789-1799
Keywords [en]
configuration interaction, excited states, X-ray spectroscopy, multiconfigurational wavefunction, computational cost
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-387717DOI: 10.1002/jcc.25832ISI: 000470013600006PubMedID: 30938847OAI: oai:DiVA.org:uu-387717DiVA, id: diva2:1330467
Funder
Knut and Alice Wallenberg Foundation, KAW-2013.0020Carl Tryggers foundation Stiftelsen Olle Engkvist ByggmästareAvailable from: 2019-06-25 Created: 2019-06-25 Last updated: 2019-06-25Bibliographically approved

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Delcey, Mickael GSörensen, Lasse KraghVacher, MorganeCouto, Rafael CarvalhoLundberg, Marcus

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