Fortenberry Ryan C, Huang Xinchuan, McCarthy Michael C, Crawford T Daniel, Lee Timothy J
Department of Chemistry, Georgia Southern University , Statesboro, Georgia 30460, United States.
J Phys Chem B. 2014 Jun 19;118(24):6498-510. doi: 10.1021/jp412362h. Epub 2014 Apr 3.
Highly accurate, coupled-cluster-based quartic force fields (QFFs) have been employed recently to provide spectroscopic reference for a myriad of molecules. Here, we are extending the same approach to provide vibrational and rotational spectroscopic reference data for the sulfur analogues of HOCO, HSCO, and HOCS, in both the cis and trans conformations as well as the D and (34)S isotopologues of each system. The resulting energies corroborate previous computations showing that trans-HSCO is the lowest-energy isomer for this system. The vibrational frequencies are computed with both second-order vibrational perturbation theory (VPT2) and vibrational configuration interaction (VCI) methods. The VPT2 and VCI QFF frequencies largely agree with one another to better than 5.0 cm(-1) (often better than 1.0 cm(-1)) and are also consistent with the type of behavior exhibited in previous studies. As such, the reference data provided here should assist in analysis of environments in which these sulfur systems may be found, including the interstellar medium, combustion flames, or laboratory simulations of either.
最近，高度精确的基于耦合簇的四次力场（QFFs）已被用于为众多分子提供光谱参考。在此，我们将采用相同的方法为HOCO、HSCO和HOCS的硫类似物提供振动和转动光谱参考数据，包括顺式和反式构象以及每个体系的D和(34)S同位素变体。所得能量证实了先前的计算结果，表明反式-HSCO是该体系能量最低的异构体。振动频率采用二阶振动微扰理论（VPT2）和振动组态相互作用（VCI）方法进行计算。VPT2和VCI QFF频率彼此高度一致，偏差优于5.0 cm⁻¹（通常优于1.0 cm⁻¹），并且也与先前研究中表现出的行为类型一致。因此，这里提供的参考数据应有助于分析可能发现这些硫体系的环境，包括星际介质、燃烧火焰或两者的实验室模拟环境。
