kth.sePublications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Complex Linear Response Functions for a Multiconfigurational Self-Consistent Field Wave Function in a High Performance Computing Environment
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Theoretical Chemistry and Biology.ORCID iD: 0009-0005-1966-3917
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Theoretical Chemistry and Biology. Division of Theoretical Chemistry, Department of Chemistry, Lund University, SE-221 00 Lund, Sweden.ORCID iD: 0000-0001-9883-3569
2023 (English)In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 19, no 17, p. 5924-5937Article in journal (Refereed) Published
Abstract [en]

We present novel developments for the highly efficient evaluation of complex linear response functions of a multiconfigurational self-consistent field (MCSCF) wave function as implemented in MultiPsi. Specifically, expressions for the direct evaluation of linear response properties at given frequencies using the complex polarization propagator (CPP) approach have been implemented, within both the Tamm-Dancoff approximation (TDA) and the random phase approximation (RPA). Purely real algebra with symmetric and antisymmetric trial vectors in a shared subspace is used wherein the linear response equations are solved. Two bottlenecks of large scale MC-CPP calculations, namely, the memory footprint and computational time, are addressed. The former is addressed by limiting the size of the subspace of trial vectors by using singular value decomposition (SVD) on either orbital or CI subspaces. The latter is addressed using an efficient parallel implementation as well as the strategy of dynamically adding linear response equations at near-convergence to neighboring roots. Furthermore, a novel methodology for decomposing MC-CPP spectra in terms of intuitive orbital excitations in an approximate fashion is presented. The performance of the code is illustrated with several numerical examples, including the X-ray spectrum of a molecule with nearly one hundred atoms. Additionally, for X-ray spectroscopy, the effect of including or excluding the core orbital in the active space on small covalent metal complexes is discussed.

Place, publisher, year, edition, pages
American Chemical Society (ACS) , 2023. Vol. 19, no 17, p. 5924-5937
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-338493DOI: 10.1021/acs.jctc.3c00317ISI: 001051314400001PubMedID: 37596971Scopus ID: 2-s2.0-85169907700OAI: oai:DiVA.org:kth-338493DiVA, id: diva2:1812149
Note

QC 20231115

Available from: 2023-11-15 Created: 2023-11-15 Last updated: 2023-11-15Bibliographically approved

Open Access in DiVA

No full text in DiVA

Other links

Publisher's full textPubMedScopus

Authority records

Scott, MikaelDelcey, Mickael G

Search in DiVA

By author/editor
Scott, MikaelDelcey, Mickael G
By organisation
Theoretical Chemistry and Biology
In the same journal
Journal of Chemical Theory and Computation
Theoretical Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
pubmed
urn-nbn

Altmetric score

doi
pubmed
urn-nbn
Total: 43 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf