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arXiv · 2302.01414

Vibrational infrared and Raman spectrum of HCOOH from variational computations

Gustavo Avila·Alberto Martín Santa Daría·Edit Mátyus
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Abstract

All vibrational energies of the (trans-, cis-, delocalized-) formic acid molecule are converged up to 4500 cm$^{-1}$ beyond the zero-point vibrational energy with the GENIUSH-Smolyak variational approach and using an ab initio potential energy surface [D. P. Tew and W. Mizukami, J. Phys. Chem. A, 120, 9815-9828 (2016)]. Full-dimensional dipole and polarizability surfaces are fitted to points computed at the CCSD/aug-cc-pVTZ level of theory. Then, body-fixed vibrational dipole and polarizability transition moments are evaluated and used to simulate jet-cooled infrared and Raman spectra of HCOOH. The benchmark-quality vibrational energy, transition moment, and wave function list will be used in further work in comparison with vibrational experiments, and in further rovibrational computations.

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Gustavo Avila, Alberto Martín Santa Daría, Edit Mátyus. 2023-02-02. Vibrational infrared and Raman spectrum of HCOOH from variational computations. https://doi.org/10.1039/d3cp00541k

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