Škoviera Ján, Černušák Ivan, Louis Florent, Neogrády Pavel
Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Mlynská dolina CH1, Ilkovičova 6, 84215, Bratislava, Slovakia.
Laboratoire de PhysicoChimie des Processus de Combustion et de l'Atmosphére (PC2A), Sciences et Technologies 1, Université Lille, Villeneuve d'Ascq, France.
J Mol Model. 2017 Nov 9;23(12):339. doi: 10.1007/s00894-017-3503-9.
Correlated ab initio methods [CASPT2 and R-CCSD(T)] in conjunction with the ANO-RCC basis sets in large contraction were used to calculate potential energy curves (PECs) of the ground and excited electronic states of CsH (doublets and quartets) with the inclusion of the scalar relativistic effects and spin-orbit interaction. The ground XΣ state is a rather fragile van der Waals molecular ion. The binding energy of this XΣ state provided by both computational methods is estimated to be 0.02-0.04 eV, and is compared with the reported experimental binding energy (0.51-0.77 eV). This large binding energy can be attributed to the AΣ state, and can thus explain the apparent disagreement between theory and experiment. The spectroscopic constants of all bound states were calculated from the PECs and compared with previous published data for XΣ and AΣ states. Graphical abstract Low-lying Ω states of cesium hydride cation.
关联的从头算方法[CASPT2和R - CCSD(T)]与大收缩的ANO - RCC基组相结合，用于计算CsH（二重态和四重态）基态和激发态电子态的势能曲线（PEC），其中包含标量相对论效应和自旋 - 轨道相互作用。基态XΣ是一个相当脆弱的范德瓦尔斯分子离子。两种计算方法给出的该XΣ态的结合能估计为0.02 - 0.04电子伏特，并与报道的实验结合能（0.51 - 0.77电子伏特）进行了比较。这种较大的结合能可归因于AΣ态，从而可以解释理论与实验之间明显的差异。所有束缚态的光谱常数均从PEC计算得出，并与先前发表的XΣ和AΣ态数据进行了比较。图形摘要 氢化铯阳离子的低能级Ω态。
