Jakub Širůček, Boris Le Guennic*, Yann Damour, Pierre-François Loos* and Denis Jacquemin*,
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We found that the d-<i>aug</i>-cc-pVTZ basis set is always adequate while its more compact double-ζ counterpart, d-<i>aug</i>-cc-pVDZ, performs well in most cases. These QR-CC3 data allow us to assess the performance of QR-TDDFT, with and without applying the Tamm-Dancoff approximation, using a panel of global and range-separated hybrids (B3LYP, BH&HLYP, CAM-B3LYP, LC-BLYP33, and LC-BLYP47), as well as several lower-order wave function methods, i.e., QR-CCSD, QR-CC2, EOM-CCSD, ISR-ADC(2), and ISR-ADC(3). We show that QR-TDDFT delivers acceptable errors for ESA oscillator strengths with CAM-B3LYP showing particular promise, especially for the largest molecules of our set, and in the Franck–Condon (FC) region. We also find that ISR-ADC(3) exhibits excellent performance in this region. When using excited-state optimal geometries, the relative performance of wave function-based approaches remains consistent with trends observed in the Franck–Condon region. However, for TD(A)-DFT, the accuracy varies more significantly, as the performance of different exchange-correlation functionals significantly depends on the chosen geometry.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":"21 9","pages":"4688–4703 4688–4703"},"PeriodicalIF":5.5000,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Excited-State Absorption: Reference Oscillator Strengths, Wave Function, and TDDFT Benchmarks\",\"authors\":\"Jakub Širůček, Boris Le Guennic*, Yann Damour, Pierre-François Loos* and Denis Jacquemin*, \",\"doi\":\"10.1021/acs.jctc.5c0015910.1021/acs.jctc.5c00159\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Excited-state absorption (ESA) corresponds to the transition between two electronic excited states and is a fundamental process for probing and understanding light-matter interactions. Accurate modeling of ESA is indeed often required to interpret time-resolved experiments. In this contribution, we present a dataset of 53 ESA oscillator strengths in three different gauges and the associated vertical transition energies between 71 excited states of 21 small- and medium-sized molecules from the QUEST database. In a few cases, we additionally investigated the effect of geometry relaxation on excited-state geometries. The reference values were obtained within the quadratic response (QR) CC3 formalism using eight different Dunning basis sets. We found that the d-<i>aug</i>-cc-pVTZ basis set is always adequate while its more compact double-ζ counterpart, d-<i>aug</i>-cc-pVDZ, performs well in most cases. These QR-CC3 data allow us to assess the performance of QR-TDDFT, with and without applying the Tamm-Dancoff approximation, using a panel of global and range-separated hybrids (B3LYP, BH&HLYP, CAM-B3LYP, LC-BLYP33, and LC-BLYP47), as well as several lower-order wave function methods, i.e., QR-CCSD, QR-CC2, EOM-CCSD, ISR-ADC(2), and ISR-ADC(3). We show that QR-TDDFT delivers acceptable errors for ESA oscillator strengths with CAM-B3LYP showing particular promise, especially for the largest molecules of our set, and in the Franck–Condon (FC) region. We also find that ISR-ADC(3) exhibits excellent performance in this region. When using excited-state optimal geometries, the relative performance of wave function-based approaches remains consistent with trends observed in the Franck–Condon region. 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Excited-State Absorption: Reference Oscillator Strengths, Wave Function, and TDDFT Benchmarks
Excited-state absorption (ESA) corresponds to the transition between two electronic excited states and is a fundamental process for probing and understanding light-matter interactions. Accurate modeling of ESA is indeed often required to interpret time-resolved experiments. In this contribution, we present a dataset of 53 ESA oscillator strengths in three different gauges and the associated vertical transition energies between 71 excited states of 21 small- and medium-sized molecules from the QUEST database. In a few cases, we additionally investigated the effect of geometry relaxation on excited-state geometries. The reference values were obtained within the quadratic response (QR) CC3 formalism using eight different Dunning basis sets. We found that the d-aug-cc-pVTZ basis set is always adequate while its more compact double-ζ counterpart, d-aug-cc-pVDZ, performs well in most cases. These QR-CC3 data allow us to assess the performance of QR-TDDFT, with and without applying the Tamm-Dancoff approximation, using a panel of global and range-separated hybrids (B3LYP, BH&HLYP, CAM-B3LYP, LC-BLYP33, and LC-BLYP47), as well as several lower-order wave function methods, i.e., QR-CCSD, QR-CC2, EOM-CCSD, ISR-ADC(2), and ISR-ADC(3). We show that QR-TDDFT delivers acceptable errors for ESA oscillator strengths with CAM-B3LYP showing particular promise, especially for the largest molecules of our set, and in the Franck–Condon (FC) region. We also find that ISR-ADC(3) exhibits excellent performance in this region. When using excited-state optimal geometries, the relative performance of wave function-based approaches remains consistent with trends observed in the Franck–Condon region. However, for TD(A)-DFT, the accuracy varies more significantly, as the performance of different exchange-correlation functionals significantly depends on the chosen geometry.
期刊介绍:
The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.