Accurate ab initio vibrational energies of methyl chloride

Owens, Alec; Yurchenko, Sergei N.; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

doi:10.1063/1.4922890

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Accurate ab initio vibrational energies of methyl chloride

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Owens, Alec
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Department of Physics and Astronomy, University College London;

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Thiel, Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Owens, A., Yurchenko, S. N., Yachmenev, A., Tennyson, J., & Thiel, W. (2015). Accurate ab initio vibrational energies of methyl chloride. The Journal of Chemical Physics, 142(24), 244306/1-244306/10. doi:10.1063/1.4922890.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0027-B623-3

Abstract

Two new nine-dimensional potential energy surfaces (PESs) have been generated using high-level ab initio theory for the two main isotopologues of methyl chloride, CH₃ ³⁵Cl and CH₃ ³⁷Cl. The respective PESs, CBS-35 ^HL, and CBS-37 ^HL, are based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set (CBS) limit, and incorporate a range of higher-level (HL) additive energy corrections to account for core-valence electron correlation, higher-order coupled cluster terms, scalar relativistic effects, and diagonal Born-Oppenheimer corrections. Variational calculations of the vibrational energy levels were performed using the computer program TROVE, whose functionality has been extended to handle molecules of the form XY ₃Z. Fully converged energies were obtained by means of a complete vibrational basis set extrapolation. The CBS-35^HL and CBS-37 ^HL PESs reproduce the fundamental term values with root-mean-square errors of 0.75 and 1.00 cm⁻¹, respectively. An analysis of the combined effect of the HL corrections and CBS extrapolation on the vibrational wavenumbers indicates that both are needed to compute accurate theoretical results for methyl chloride. We believe that it would be extremely challenging to go beyond the accuracy currently achieved for CH₃Cl without empirical refinement of the respective PESs.