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Accurate ab initio vibrational energies of methyl chloride

MPG-Autoren
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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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Zitation

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.


Zitierlink: http://hdl.handle.net/11858/00-001M-0000-0027-B623-3
Zusammenfassung
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-35HL 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.