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Two‐ and one‐photon absorption spectra of aqueous thiocyanate anion highlight the role of symmetry in the condensed phase.

Authors :
Sarangi, Ronit
Nanda, Kaushik D.
Krylov, Anna I.
Source :
Journal of Computational Chemistry. 5/5/2024, Vol. 45 Issue 12, p878-885. 8p.
Publication Year :
2024

Abstract

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. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
01928651
Volume :
45
Issue :
12
Database :
Academic Search Index
Journal :
Journal of Computational Chemistry
Publication Type :
Academic Journal
Accession number :
176198130
Full Text :
https://doi.org/10.1002/jcc.27282