Calculation of rovibrational line intensities within vibrational configuration interaction (VCI) theory

由于系外行星的发现，天体化学进入了公众的意识，因此对小分子的光谱研究在过去十年中经历了一次复兴。这些研究伴随着量子化学模拟，这为这些系统的物理特性提供了实质性的见解，并允许分析相当复杂的光谱。在之前的项目中，基于VSCF/VCI理论和Watson哈密顿量开发了一个新的从头算程序，用于自动计算旋转振动红外和拉曼光谱，该程序允许以几乎黑盒式的方式精确计算旋转振动光谱。然而，该程序在自动化和效率方面尚未完全优化，并且缺乏一些理想的功能，例如热带的计算。这些主题和挑战性分子的研究是本更新提案的主题。

Due to the discovery of exoplanets astrochemistry moved into the awareness of the public and thus spectroscopic investigations on small molecules experienced a renaissance within the last decade. These studies are accompanied by quantum chemical simulations, which provide substantial insight into the physics of these systems and which allow to analyze the rather complex spectra. Within the previous project a new ab initio program for an automated calculation of rovibrational infrared and Raman spectra based on VSCF/VCI theory and the Watson Hamiltonian has been developed, which allows for the accurate calculation of rovibrational spectra in an almost black-box type fashion. However, this program has not yet fully been optimized with respect to automatization and efficiency and lacks some desirable features as for example the calculation of hot bands. These topics and the investigation of challenging molecules are subject of this renewal proposal.