Wang Yongtian, Han Changcai, Hong Jing, Fei Zejie, Dong Changwu, Liu Hongtao, Xiong Xiaogen
Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences Shanghai 201800 P. R. China
University of Chinese Academy of Sciences Beijing 100049 P. R. China.
RSC Adv. 2021 May 24;11(31):18729-18736. doi: 10.1039/d1ra03173b.
The electronic structure and vibrational spectrum of the VOH anion are explored by combining photoelectron imaging spectroscopy and density functional theoretical (DFT) calculations. The electron affinity (EA) of VOH is determined to be 1.304 ± 0.030 eV from the vibrationally resolved photoelectron spectrum acquired at 1.52 eV (814 nm). The anisotropy parameter () for the EA defined peak is measured to be 1.63 ± 0.10, indicating that it is the 17a' (4s orbital of the vanadium atom) electron attachment leading to the formation of the ground state of the VOH anion. The vibrational fundamentals , , and are obtained for the neutral ground state. Experimental assignments are confirmed by energies from electronic structure calculations and Franck-Condon (FC) spectral simulations. These simulations support assigning the anion ground state as the results obtained from the B3LYP method. In addition, the molecular orbitals and bonding involved in the anionic VOH cluster are also examined based on the present theoretical calculations.
通过结合光电子成像光谱和密度泛函理论（DFT）计算，研究了VOH阴离子的电子结构和振动光谱。根据在1.52 eV（814 nm）处获得的振动分辨光电子能谱，确定VOH的电子亲和能（EA）为1.304±0.030 eV。测量得到EA定义峰的各向异性参数（）为1.63±0.10，表明是17a'（钒原子的4s轨道）电子附着导致形成VOH阴离子的基态。获得了中性基态的振动基频、、和。电子结构计算的能量和弗兰克-康登（FC）光谱模拟证实了实验归属。这些模拟支持将阴离子基态指定为从B3LYP方法获得的结果。此外，还基于当前的理论计算研究了阴离子VOH簇中涉及的分子轨道和键合。
