Two- and one-photon absorption spectra of aqueous thiocyanate anion highlight the role of symmetry in the condensed phase
© 2023 Wiley Periodicals LLC.
| Publié dans: | Journal of computational chemistry. - 1984. - 45(2024), 12 vom: 05. Mai, Seite 878-885 |
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| Auteur principal: | |
| Autres auteurs: | , |
| Format: | Article en ligne |
| Langue: | English |
| Publié: |
2024
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| Accès à la collection: | Journal of computational chemistry |
| Sujets: | Journal Article charge‐transfer‐to‐solvent states computational spectroscopy equation‐of‐motion coupled‐cluster molecular orbital theory two‐photon spectroscopy wave‐function analysis |
| Résumé: | © 2023 Wiley Periodicals LLC. We present the two-photon absorption (2PA) spectrum of aqueous thiocyanate calculated using high-level quantum-chemistry methods. The 2PA spectrum is compared to the one-photon absorption (1PA) spectrum computed using the same computational protocol. Although the two spectra probe the same set of electronic states, the intensity patterns are different, leading to an apparent red-shift of the 2PA spectrum relative to the 1PA spectrum. The presented analysis explains the intensity patterns and attributes the differences between the 1PA and 2PA spectra to the native symmetry of isolated SCN - , which influences the spectra in the low-symmetry solvated environment. The native symmetry also manifests itself in variations of the polarization ratio (e.g., parallel vs. perpendicular cross sections) across the spectrum. The presented results highlight the potential of 2PA spectroscopy and high-level quantum-chemistry methods in studies of condensed-phase phenomena |
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| Description: | Date Revised 21.03.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.27282 |