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Theoretical Study of Infrared Spectra of OCS-(pH2)2, OCS-(oD2)2, OCS-(HD)2, and Mixed OCS-pH2-He Trimers
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-03-01 00:00:00 , DOI: 10.1021/acs.jpca.7b12708
Jing-Min Liu 1 , Xiao-Long Zhang 1 , Yu Zhai 1 , Hui Li 1
Affiliation  

The calculated rovibrational energy levels and infrared spectra for OCS-(pH2)2, OCS-(oD2)2, OCS-(HD)2 and mixed OCS-pH2-He trimers are obtained by performing the exact basis-set calculations for the first time based on the newly developed potential energy surfaces (J. Chem. Phys.2017, 147, 044313). The “adiabatic-hindered-rotor” (AHR) method is used for reduced-dimension treatment of the hydrogen rotation. The predicted band origin shifts and the infrared spectra are in good agreement with the available experimental values: for the band origin shifts and infrared transitions, the root-mean-square(rms) deviations are smaller than 0.044 and 0.002 cm–1, respectively. We extend the assignments to the unrecorded infrared transitions for OCS-(pH2)2 and OCS-(HD)2 complexes and identify the infrared spectra for OCS-(oD2)2 and OCS-pH2-He for the first time. Three-dimensional density distributions for the ground states of OCS-(pH2)2, OCS-pH2-He, and OCS-(He)2 show that the pH2 molecules are localized in their corresponding global minimum regions, while the pronounced locations of the He atoms are missing in OCS-pH2-He and OCS-(He)2 with forming incomplete circles around the OCS axis. A clear tunneling splitting is observed for the torsional motion of the two hydrogen molecules (pH2, HD, or oD2) on a ring about the OCS molecular axis, whereas no tunneling splitting is found in OCS-pH2-He or OCS-(He)2 due to a much lower torsional barrier.

中文翻译:

OCS-(p H 22,OCS-(o D 22,OCS-(HD)2和混合的OCS- p H 2 -He三聚体的红外光谱的理论研究

通过计算精确的基数,可以获得OCS-(p H 22,OCS-(o D 22,OCS-(HD)2和混合的OCS- p H 2 -He三聚体的振动能级和红外光谱。-set计算用于基于新开发的势能面(在第一时间J.化学物理。2017年,147,044313)。“绝热受阻转子”(AHR)方法用于氢旋转的降维处理。预测的谱带原点偏移和红外光谱与可用的实验值非常吻合:对于谱带原点偏移和红外跃迁​​,均方根(rms)偏差分别小于0.044和0.002 cm –1。我们将赋值扩展到OCS-(p H 22和OCS-(HD)2复合物的未记录的红外跃迁,并确定OCS-(o D 22和OCS- p H 2的红外光谱-他第一次。OCS-(p H 22,OCS- p H 2 -He和OCS-(He)2基态的三维密度分布表明,p H 2分子位于其相应的全局最小区域中,而在OCS- p H 2 -He和OCS-(He)2中缺少He原子的明显位置,并围绕OCS轴形成不完整的圆。对于两个氢分子(p H 2,HD或o D 2)在围绕OCS分子轴的环上,而由于低得多的扭转势垒,在OCS- p H 2 -He或OCS-(He)2中没有发现隧道分裂。
更新日期:2018-03-01
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