Rodriguez Arianna, Han Jiande, Yan Jiarui, Heaven Michael C, Cheng Lan
Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
J Chem Phys. 2025 Jan 14;162(2). doi: 10.1063/5.0245862.
Electronic spectra for OThF have been recorded using fluorescence excitation and two-photon resonantly enhanced ionization techniques. Multiple vibronic bands were observed in the 340-460 nm range. Dispersed fluorescence spectra provided ground state vibrational constants and evidence of extensive vibronic state mixing at higher excitation energies. Two-photon ionization measurements established the ionization energy for OThF of 6.283(5) eV. To guide the assignment of the OThF spectra, electronic structure calculations were carried out using relativistic equation-of-motion coupled-cluster singles and doubles methods. These calculations indicated that spin-orbit induced mixing of the 32A″ and 42A' states was mediated by a seam of potential energy surface intersections.
已使用荧光激发和双光子共振增强电离技术记录了OThF的电子光谱。在340 - 460纳米范围内观察到多个振动电子带。色散荧光光谱提供了基态振动常数，并证明了在较高激发能量下存在广泛的振动电子态混合。双光子电离测量确定了OThF的电离能为6.283(5)电子伏特。为了指导OThF光谱的归属，使用相对论运动方程耦合簇单双激发方法进行了电子结构计算。这些计算表明，自旋轨道诱导的32A″和42A'态的混合是由势能面交叉缝介导的。
