College of Environmental Sciences and Engineering, Dalian Maritime University, 1 Linghai Road, Dalian, Liaoning 116026, People's Republic of China.
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, 457 Zhongshan Road, Dalian, Liaoning 116023, People's Republic of China.
J Chem Phys. 2018 Mar 28;148(12):124301. doi: 10.1063/1.5022108.
Photodissociation dynamics of HO via the F̃ state at 111.5 nm were investigated using the high resolution H-atom Rydberg "tagging" time-of-flight (TOF) technique, in combination with the tunable vacuum ultraviolet free electron laser at the Dalian Coherent Light Source. The product translational energy distributions and angular distributions in both parallel and perpendicular directions were derived from the recorded TOF spectra. Based on these distributions, the quantum state distributions and angular anisotropy parameters of OH (X) and OH (A) products have been determined. For the OH (A) + H channel, highly rotationally excited OH (A) products have been observed. These products are ascribed to a fast direct dissociation on the B̃A state surface after multi-step internal conversions from the initial excited F̃ state to the B̃ state. While for the OH (X) + H channel, very highly rotationally excited OH (X) products with moderate vibrational excitation are revealed and attributed to the dissociation via a nonadiabatic pathway through the well-known two conical intersections between the B̃-state and the X̃-state surfaces.
使用高分辨率 H 原子里德堡“标记”飞行时间 (TOF) 技术,结合大连相干光源的可调谐真空紫外自由电子激光,研究了 111.5nm 处 F̃态的 HO 的光解动力学。从记录的 TOF 光谱中推导出了平行和垂直方向的产物平移能分布和角分布。基于这些分布,确定了 OH(X)和 OH(A)产物的量子态分布和角各向异性参数。对于 OH(A)+H 通道,观察到高度转动激发的 OH(A)产物。这些产物归因于从初始激发的 F̃态到 B̃态的多步内转化后,快速直接在 B̃A 态表面上解离。对于 OH(X)+H 通道,揭示了具有中等振动激发的非常高度转动激发的 OH(X)产物,并归因于通过 B̃态和 X̃态表面之间众所周知的两个双锥形交叉点的非绝热途径的解离。