Quantification of the Ionic Character of Multiconfigurational Wave Functions: The


Journal

The journal of physical chemistry. A
ISSN: 1520-5215
Titre abrégé: J Phys Chem A
Pays: United States
ID NLM: 9890903

Informations de publication

Date de publication:
23 Nov 2023
Historique:
medline: 18 10 2023
pubmed: 18 10 2023
entrez: 18 10 2023
Statut: ppublish

Résumé

The complete active space self-consistent field (CASSCF) method is a cornerstone in modern excited-state quantum chemistry providing the starting point for most common multireference computations. However, CASSCF, when used with a minimal active space, can produce significant errors (>2 eV) even for the excitation energies of simple hydrocarbons if the states of interest possess ionic character. After illustrating this problem in some detail, we present a diagnostic for ionic character, denoted as

Identifiants

pubmed: 37851528
doi: 10.1021/acs.jpca.3c05559
pmc: PMC10683019
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

9842-9852

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Auteurs

Silmar A do Monte (SA)

Departamento de Química, CCEN, Universidade Federal da Paraíba, 58051-900 João Pessoa, Brazil.

Rene F K Spada (RFK)

Departamento de Física, Instituto Tecnológico de Aeronáutica, 12.228-900 São José dos Campos, São Paulo, Brazil.

Rodolpho L R Alves (RLR)

Departamento de Química, CCEN, Universidade Federal da Paraíba, 58051-900 João Pessoa, Brazil.

Lachlan Belcher (L)

Departamento de Física, Instituto Tecnológico de Aeronáutica, 12.228-900 São José dos Campos, São Paulo, Brazil.

Ron Shepard (R)

Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.

Hans Lischka (H)

Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, United States.

Felix Plasser (F)

Department of Chemistry, Loughborough University, Loughborough LE11 3TU, U.K.

Classifications MeSH