Fundamental Vibrational Frequencies of Isolated 2-Phosphaethynolate and 2-Phosphaethynthiolate Anions: Ocp– and Scp–
Abstract
Both second-order vibrational perturbation theory (VPT2) and vibrational configuration interaction (VCI) theory have been employed to compute the fundamental vibrational frequencies of the isolated 2-phosphaethynolate and 2-phosphaethynthiolate anions (OCP (Formula presented.) and SCP (Formula presented.)) near the CCSD(T) complete basis set (CBS) limit. Our best estimates of the fundamental frequency associated with the doubly degenerate bending mode of these linear triatomic ions ((Formula presented.)) are 492 cm (Formula presented.) for OCP (Formula presented.) and 362 cm (Formula presented.) for SCP (Formula presented.). Due to strong coupling, the stretching motions of SCP (Formula presented.) are best described as pseudo-symmetric ((Formula presented.)) and pseudo-antisymmetric ((Formula presented.)) stretches that we estimate to be 588 cm (Formula presented.) and 1367 cm (Formula presented.), respectively. For OCP (Formula presented.), our best predictions are 792 cm (Formula presented.) for (Formula presented.) and 1795 cm (Formula presented.) for (Formula presented.), with the latter having predominantly CO stretching character. In the absence of experimental gas-phase vibrational spectra for these species, these computed anharmonic frequencies provide important reference values to help quantify spectroscopic perturbations induced by environmental effects such as those from solvents or counter ions.
Recommended Citation
K. R. Barlow et al., "Fundamental Vibrational Frequencies of Isolated 2-Phosphaethynolate and 2-Phosphaethynthiolate Anions: Ocp– and Scp–," Molecular Physics, vol. 119, no. 21 thru 22, article no. e1967495, Taylor and Francis Group; Taylor and Francis, Jan 2021.
The definitive version is available at https://doi.org/10.1080/00268976.2021.1967495
Department(s)
Chemistry
Keywords and Phrases
2-phosphaethynolate anion (OCP); 2-phosphaethynthiolate anion (SCP); anharmonic fundamental vibrational frequencies; second-order vibrational perturbation theory (VPT2); vibrational configuration interaction (VCI) theory
International Standard Serial Number (ISSN)
1362-3028; 0026-8976
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2024 Taylor and Francis Group; Taylor and Francis, All rights reserved.
Publication Date
01 Jan 2021
Comments
National Science Foundation, Grant CHE-1664998