Vibrational infrared and Raman spectra of HCOOH from variational computations
Gustavo Avila1, Alberto Martín Santa Daría1,2, Edit Mátyus1
1ELTE, Eötvös Loránd University, Institute of Chemistry, Pázmány Péter sétány 1/A, 1117 Budapest, Hungary. edit.matyus@ttk.elte.hu.
Abstract:
All vibrational energies of the formic acid molecule in different forms (trans-, cis-, delocalized-) were 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)]. The full-dimensional dipole and polarizability surfaces were fitted to points computed at the CCSD/aug-cc-pVTZ level of theory. Then, body-fixed vibrational dipole and polarizability transition moments were evaluated and used to simulate jet-cooled infrared and Raman spectra of HCOOH. The benchmark-quality vibrational energy, transition moment, and wave function data will be used in further work for comparison with vibrational experiments, and in further rovibrational computations.
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