title: Protonated carbonyl sulfide: prospects for the spectroscopic observation of the elusive HSCO+ isomer.
abstract: Spurred by the apparent conflict between ab initio predictions and infrared spectroscopic evidence regarding the relative stability of isomers of protonated carbonyl sulfide, key stationary points on the isomerization surface of HOCS(+) have been examined via systematic extrapolations of ab initio energies. Electron correlation has been accounted for using second-order Møller-Plesset perturbation theory and coupled cluster theory through triple excitations [CCSD, CCSD(T), and CCSDT] in conjunction with the correlation consistent hierarchy of basis sets, cc-pVXZ (X=D,T,Q,5,6). HSCO(+) is predicted to lie lower in energy than HOCS(+) by 4.86 kcal mol(-1), computed using the focal point extrapolation scheme of Allen and co-workers [J. Chem. Phys. 99, 4638 (1993)] with corrections for anharmonic zero-point vibrational energy, core correlation, non-Born-Oppenheimer, and scalar relativistic effects. A transition state has been located, constituting the barrier to isomerization of HSCO(+) to HOCS(+), lying 68.9 kcal mol(-1) higher in energy than HSCO(+). This is well above predicted exothermicity [DeltaH(r) (o)(0 K)=48.1 kcal mol(-1), cc-pVQZ CCSD(T)] for the reaction considered in the experiments (HSCO(+)+H(2)-->OCS+H(3) (+)). Though proton tunneling will lead to a lower effective barrier, this prediction is consistent with the lack of HSCO(+) in electrical discharges in H(2)OCS, since the relative populations of HOCS(+) and HSCO(+) will depend on the experimental details of the protonation route rather than the relative thermodynamic stability of the isomers. Anharmonic vibrational frequencies and vibrationally corrected rotational constants from cc-pVTZ CCSD(T) cubic and quartic force constants are provided, to aid in the spectroscopic observation of the energetically favorable but apparently elusive HSCO(+) isomer.
authors.affiliation: Center for Computational Chemistry, University of Georgia, Athens, Georgia 30602, USA.
authors.forename: Steven E
authors.initials: SE
authors.lastname: Wheeler
authors.forename: Yukio
authors.initials: Y
authors.lastname: Yamaguchi
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer