Ground- and Excited-State Dipole Moments and Oscillator Strengths of Full Configuration Interaction Quality

We report ground- and excited-state dipole moments and oscillator strengths (computed in different “gauges” or representations) of full configuration interaction (FCI) quality using the selected configuration interaction method known as Configuration Interaction using a Perturbative Selection made I...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2023-01, Vol.19 (1), p.221-234
Main Authors: Damour, Yann, Quintero-Monsebaiz, Raúl, Caffarel, Michel, Jacquemin, Denis, Kossoski, Fábris, Scemama, Anthony, Loos, Pierre-François
Format: Article
Language:English
Subjects:
Chemical Sciences
Computation
Configuration interaction
Dipole moments
Excitation
Gauges
or physical chemistry
Oscillator strengths
Oscillators
Quantum Electronic Structure
Theoretical and
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Summary:We report ground- and excited-state dipole moments and oscillator strengths (computed in different “gauges” or representations) of full configuration interaction (FCI) quality using the selected configuration interaction method known as Configuration Interaction using a Perturbative Selection made Iteratively (CIPSI). Thanks to a set encompassing 35 ground- and excited-state properties computed in 11 small molecules, the present near-FCI estimates allow us to assess the accuracy of high-order coupled-cluster (CC) calculations including up to quadruple excitations. In particular, we show that incrementing the excitation degree of the CC expansion (from CC with singles and doubles (CCSD) to CC with singles, doubles, and triples (CCSDT) or from CCSDT to CC with singles, doubles, triples, and quadruples (CCSDTQ)) reduces the average error with respect to the near-FCI reference values by approximately 1 order of magnitude.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.2c01111