Ab initio simulation of matrix-isolation vibrational spectroscopy

在混合量子经典模拟的框架下，我们开发了一个计算方案来研究嵌入在稀有气体基质环境中的目标分子的振动位移。高水平从头计算被用来确定构建系统总势所需的相互作用势，并用这个势进行了蒙特卡罗模拟，以便在周围稀有气体原子存在的情况下获得振动光谱。研究了NgBeO(Ng=Ar，Xe)和HXeCl在不同稀有气体基质中的振动位移，并详细讨论了光谱位移的来源。这项工作表明，对周围稀有气体原子的显式处理对于重现实验中观察到的振动位移是必不可少的。

We have developed a computational scheme to investigate the vibrational shift of a target molecule embedded in noble-gas matrix environments in the framework of the mixed quantum-classical simulations. The high-level ab initio calculations were carried out to determine the interaction potential needed to construct the total potential of the system, and the Monte Carlo simulations were performed using this potential in order to obtain vibrational spectra in the presence of surrounding noble-gas atoms. The vibrational shifts of NgBeO (Ng=Ar, Xe) and HXeCl in various noble-gas matrices were investigated and the origin of the spectral shifts were discussed in detail. From this work, it was shown that the explicit treatment of the surrounding noble-gas atoms is essential to reproduce the experimentally observed vibrational shifts.