本项目通过高分辨紫外激光诱导碎片光谱，结合计算化学，探索二价金属离子-分子配合物体系的微观结构、激发态性质、离子-分子相互作用规律。实验方面，采用激光电离和超声冷流分子束技术制备二价金属配合物离子。采用四极杆-离子阱串联质谱和波长可调激光器记录光致解离碎片高分辨光谱。计算方面，采用密度泛函(DFT)方法计算二价金属配合物离子的电子基态、微观结构、结合能等。采用时间依赖密度泛函（TDDFT）方法计算电子垂直激发能量和相应振子强度。针对高分辨光谱、TDDFT计算方法、二价金属离子配合物微观结构、化学性质、金属离子与配体分子相互作用规律、自旋污染和非物理激发对TDDFT计算的影响等关键科学问题进行研究。发展了DFT/TDDFT计算理论，将其有效应用于二价金属离子配合物体系微观结构与化学性质的计算和科学分析。

This project is focusing on metal dication complexes in the gas phase. Modified experimental techniques for recording spectra in the gas phase are combined with the theoretical methods required to interpret the spectra of metal dication complexes, which reviews how metal ion-molecule might promote chemical reactions. For experimental section, it attempts to identify two aspects of barriers. First, difficulties that might exist to measuring the optical spectra of metal dication complexes using current ion beam technology. Secondly, estimates of photofragment yields based on typical absorption cross sections and the kinetics of fragmentation highlight the difficulties involved in measuring such spectra. A typical experiment will involve measuring either photofragment yield or ion beam depletion as function of laser wavelength. Of the theoretical part, method for calculating spectral transitions in metal complexes is time-dependent density functional theory (TDDFT). It is shown that although TDDFT is for the most part satisfactory, extreme caution should be exercised when investigating the electronic states of open-shell complexes. A theoretical method that predicts the correct ground state geometry of an open-shell complex does not necessarily yield the correct electronically excited states due to multi-electron character and/or spin contamination in the excited state manifold. This project is attempt to develop experimental techniques for recording more accurate “electronic state resolved” or/and "conformation resolved"spectra, which will provide new and more demanding benchmarks for refinement of theoretical methods.