title: Fundamental vibrational frequencies and spectroscopic constants of HOCS+, HSCO+, and isotopologues via quartic force fields.
abstract: Besides the ν(1) O-H stretching mode at 3435 cm(-1) for HOCS(+), the fundamental vibrational frequencies for this cation and its HSCO(+) isomer have not been determined experimentally. Because these systems are analogues to HOCO(+), a detected interstellar molecule, and are believed to play an important role in reactions of OCS, which has also been detected in the interstellar medium, these cations are of importance to interstellar chemistry and reaction surface studies. This work provides the fundamental vibrational frequencies and spectroscopic constants computed with vibrational perturbation theory (VPT) at second order and the vibrational configuration interaction (VCI) method conjoined with the most accurate quartic force field (QFF) applied to date for these systems. Our computations match experiment to better than 2 cm(-1) for the known O-H stretch. Additionally, there is strong agreement in the prediction of the fundamentals across methods and choices of QFFs. The consistency in the computations and the correspondence for the known mode should give accurate reference data for the rovibrational spectra of these cations and their singly substituted isotopologues for D, (18)O, and (34)S.
authors.affiliation: NASA Ames Research Center, Moffett Field, California 94035-1000, USA. Ryan.C.Fortenberry@nasa.gov
authors.forename: Ryan C
authors.initials: RC
authors.lastname: Fortenberry
authors.forename: Xinchuan
authors.initials: X
authors.lastname: Huang
authors.forename: Joseph S
authors.initials: JS
authors.lastname: Francisco
authors.forename: T Daniel
authors.initials: TD
authors.lastname: Crawford
authors.forename: Timothy J
authors.initials: TJ
authors.lastname: Lee