论文标题
甲基阳离子的振动分析 - 稀有气原子复合物：ch $ _3^+$ - rg（rg = he，ne，ar，ar，kr）
Vibrational analysis of methyl cation - rare gas atom complexes: CH$_3^+$-Rg (Rg=He, Ne, Ar, Kr)
论文作者
论文摘要
简单CH $ _3^+$ - RG（RG = HE，NE，AR，KR）复合物的振动光谱已通过振动构型相互作用（VCI）理论研究，这些理论依赖于多维势能表面（PES）从明确相关的群集群集计算中获得的多维势能表面（PES）进行了研究。与实验结果一致，一系列稀有气体原子会导致相当不合理的结果，并表明氦络合物的巨大零点振动能效应。为了更一致地研究这些敏感的复合物，我们还引入了配置平均振动自洽场理论（CAVSCF），这是对几种配置的标准VSCF理论的概括。将复合物的振动光谱与甲基阳离子的振动光谱进行了比较，甲基阳离子是由于标量相关效应，高级耦合群集术语，即CCSDTQ和核心价相关性而引起的。 Ch $ _3^+$的振动地面的隧道分割的发生 - 他已根据半经典的Instanton理论进行了调查。这些计算和沿固有反应坐标（IRC）与氢阳离子的能量曲线的直接比较，h $ _3 $ o $ $^+$，表明振动激发态的隧道效应应该很小。
The vibrational spectra of simple CH$_3^+$-Rg (Rg=He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction (VCI) theory relying on multidimensional potential energy surfaces (PES) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with experimental results, the series of rare gas atoms leads to rather unsystematic results and indicates huge zero point vibrational energy effects for the helium complex. In order to study these sensitive complexes more consistently, we also introduce configuration averaged vibrational self-consistent field theory (CAVSCF), which is a generalization of standard VSCF theory to several configurations. The vibrational spectra of the complexes are compared to that of the methyl cation, for which corrections due to scalar-relativistic effects, high-level coupled-cluster terms, i.e. CCSDTQ, and core-valence correlation have explicitly been accounted for. The occurrence of tunneling splittings for the vibrational ground-state of CH$_3^+$-He has been investigated on the basis of semiclassical instanton theory. These calculations and a direct comparison of the energy profiles along the intrinsic reaction coordinates (IRC) with that of the hydronium cation, H$_3$O$^+$, suggest that tunneling effects for vibrationally excited states should be very small.
