Ab initio vibrational spectroscopy of cis- and trans-Formic acid from a global potential energy surface

David P. Tew, Wataru Mizukami

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

A global analytic potential energy surface for the ro-vibrational dynamics of cis- and trans-formic acid is presented, constructed using LASSO-based regression to reproduce CCSD(T)(F12*)/cc-pVTZ-F12 energies. The fit is accurate to 0.25% has an RMS deviation from the ab initio data of 9 cm−1 for the energy range 0−15000 cm−1. Converged J = 0 vibrational eigenstates are reported, computed using vibrational configuration interaction with an internal coordinate path Hamiltonian for the torsional motion connecting the cis and trans rotamers. Methodological choices concerning the appropriate definitions of the curvilinear and diabatic bath coordinates are discussed. The zero point of the cis rotamer is 1412 cm−1 above that of the trans, which lies at 7354 cm−1. The computed fundamentals match the bands recorded from gas-phase IR spectroscopy with an RMSD of only 3 cm−1. A fresh assignment of the overtone spectra of both the cis and trans rotamers is presented for the energy range 0−4720 cm−1, where 14 out of the 51 bands are reassigned on the basis of the VCI calculations.

Original languageEnglish
Pages (from-to)9815-9828
Number of pages14
JournalJournal of Physical Chemistry A
Volume120
Issue number49
DOIs
Publication statusPublished - Jan 1 2016
Externally publishedYes

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formic acid
Hamiltonians
Vibrational spectroscopy
Potential energy surfaces
Infrared spectroscopy
Gases
potential energy
spectroscopy
configuration interaction
energy
regression analysis
baths
eigenvectors
vapor phases
deviation
harmonics

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Ab initio vibrational spectroscopy of cis- and trans-Formic acid from a global potential energy surface. / Tew, David P.; Mizukami, Wataru.

In: Journal of Physical Chemistry A, Vol. 120, No. 49, 01.01.2016, p. 9815-9828.

Research output: Contribution to journalArticle

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AB - A global analytic potential energy surface for the ro-vibrational dynamics of cis- and trans-formic acid is presented, constructed using LASSO-based regression to reproduce CCSD(T)(F12*)/cc-pVTZ-F12 energies. The fit is accurate to 0.25% has an RMS deviation from the ab initio data of 9 cm−1 for the energy range 0−15000 cm−1. Converged J = 0 vibrational eigenstates are reported, computed using vibrational configuration interaction with an internal coordinate path Hamiltonian for the torsional motion connecting the cis and trans rotamers. Methodological choices concerning the appropriate definitions of the curvilinear and diabatic bath coordinates are discussed. The zero point of the cis rotamer is 1412 cm−1 above that of the trans, which lies at 7354 cm−1. The computed fundamentals match the bands recorded from gas-phase IR spectroscopy with an RMSD of only 3 cm−1. A fresh assignment of the overtone spectra of both the cis and trans rotamers is presented for the energy range 0−4720 cm−1, where 14 out of the 51 bands are reassigned on the basis of the VCI calculations.

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