Dipartimento di Chimica "Giacomo Ciamician," Università di Bologna, via F. Selmi 2, 40126 Bologna, Italy.
Department Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
J Chem Phys. 2023 May 7;158(17). doi: 10.1063/5.0148810.
Despite their chemical simplicity, the spectroscopic investigation of light hydrides, such as hydrogen sulfide, is challenging due to strong hyperfine interactions and/or anomalous centrifugal-distortion effects. Several hydrides have already been detected in the interstellar medium, and the list includes H2S and some of its isotopologues. Astronomical observation of isotopic species and, in particular, those bearing deuterium is important to gain insights into the evolutionary stage of astronomical objects and to shed light on interstellar chemistry. These observations require a very accurate knowledge of the rotational spectrum, which is so far limited for mono-deuterated hydrogen sulfide, HDS. To fill this gap, high-level quantum-chemical calculations and sub-Doppler measurements have been combined for the investigation of the hyperfine structure of the rotational spectrum in the millimeter- and submillimeter-wave region. In addition to the determination of accurate hyperfine parameters, these new measurements together with the available literature data allowed us to extend the centrifugal analysis using a Watson-type Hamiltonian and a Hamiltonian-independent approach based on the Measured Active Ro-Vibrational Energy Levels (MARVEL) procedure. The present study thus permits to model the rotational spectrum of HDS from the microwave to far-infrared region with great accuracy, thereby accounting for the effect of the electric and magnetic interactions due to the deuterium and hydrogen nuclei.
尽管轻氢化物(如硫化氢)的化学结构简单,但由于强超精细相互作用和/或异常离心变形效应,其光谱研究具有挑战性。已经在星际介质中检测到几种氢化物,其中包括 H2S 和它的一些同位素。对同位素物种的天文观测,特别是对含有氘的同位素物种的观测,对于了解天体的演化阶段和揭示星际化学非常重要。这些观测需要对旋转光谱有非常精确的了解,而目前对于单氘化硫化氢 HDS 的旋转光谱了解有限。为了填补这一空白,已经结合了高精度量子化学计算和亚多普勒测量,以研究毫米和亚毫米波段旋转光谱的超精细结构。除了确定准确的超精细参数外,这些新的测量结果以及可用的文献数据,使我们能够使用 Watson 型哈密顿量和基于 Measured Active Ro-Vibrational Energy Levels (MARVEL) 过程的哈密顿量独立方法扩展离心分析。因此,本研究能够非常精确地模拟 HDS 的旋转光谱,从微波到远红外区域,从而考虑到由于氘核和氢核引起的电和磁相互作用的影响。