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Title: Vibrational analysis of methyl cation—Rare gas atom complexes: CH + 3—Rg (Rg = He, Ne, Ar, Kr)

Abstract

The vibrational spectra of simple CH + 3—Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on multidimensional potential energy surfaces (PESs) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with experimental results, the series of rare gas atoms leads to rather unsystematic results and indicates huge zero point vibrational energy effects for the helium complex. In order to study these sensitive complexes more consistently, we also introduce configuration averaged vibrational self-consistent field theory, which is a generalization of standard vibrational self-consistent field theory to several configurations. The vibrational spectra of the complexes are compared to that of the methyl cation, for which corrections due to scalar-relativistic effects, high-order coupled-cluster terms, e.g., quadruple excitations, and core-valence correlation have explicitly been accounted for. The occurrence of tunneling splittings for the vibrational ground-state of CH + 3 —He has been investigated on the basis of semiclassical instanton theory. Furthermore these calculations and a direct comparison of the energy profiles along the intrinsic reaction coordinates with that of the hydronium cation, H 3O +, suggest that tunneling effects for vibrationally excited states should be very small.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]
  1. Univ. of Stuttgart, Stuttgart (Germany); Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Univ. of Stuttgart, Stuttgart (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1504573
Grant/Contract Number:  
AC02-76SF00515; RA 656/25-1
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Meisner, Jan, Hallmen, Philipp P., Kästner, Johannes, and Rauhut, Guntram. Vibrational analysis of methyl cation—Rare gas atom complexes: CH+3—Rg (Rg = He, Ne, Ar, Kr). United States: N. p., 2019. Web. doi:10.1063/1.5084100.
Meisner, Jan, Hallmen, Philipp P., Kästner, Johannes, & Rauhut, Guntram. Vibrational analysis of methyl cation—Rare gas atom complexes: CH+3—Rg (Rg = He, Ne, Ar, Kr). United States. doi:10.1063/1.5084100.
Meisner, Jan, Hallmen, Philipp P., Kästner, Johannes, and Rauhut, Guntram. Wed . "Vibrational analysis of methyl cation—Rare gas atom complexes: CH+3—Rg (Rg = He, Ne, Ar, Kr)". United States. doi:10.1063/1.5084100.
@article{osti_1504573,
title = {Vibrational analysis of methyl cation—Rare gas atom complexes: CH+3—Rg (Rg = He, Ne, Ar, Kr)},
author = {Meisner, Jan and Hallmen, Philipp P. and Kästner, Johannes and Rauhut, Guntram},
abstractNote = {The vibrational spectra of simple CH+3—Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on multidimensional potential energy surfaces (PESs) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with experimental results, the series of rare gas atoms leads to rather unsystematic results and indicates huge zero point vibrational energy effects for the helium complex. In order to study these sensitive complexes more consistently, we also introduce configuration averaged vibrational self-consistent field theory, which is a generalization of standard vibrational self-consistent field theory to several configurations. The vibrational spectra of the complexes are compared to that of the methyl cation, for which corrections due to scalar-relativistic effects, high-order coupled-cluster terms, e.g., quadruple excitations, and core-valence correlation have explicitly been accounted for. The occurrence of tunneling splittings for the vibrational ground-state of CH+3 —He has been investigated on the basis of semiclassical instanton theory. Furthermore these calculations and a direct comparison of the energy profiles along the intrinsic reaction coordinates with that of the hydronium cation, H3O+, suggest that tunneling effects for vibrationally excited states should be very small.},
doi = {10.1063/1.5084100},
journal = {Journal of Chemical Physics},
number = 8,
volume = 150,
place = {United States},
year = {2019},
month = {2}
}

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