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AsH_3 Ultraviolet Photochemistry

机译:AsH_3紫外线光化学

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摘要

High-n Rydberg time-of-flight spectroscopy has been used to study the 193.3 nm photolysis of AsH_3. The center-of-mass translational energy distribution for the 1-photon process, AsH_3 + hv → AsH_2 + H, P(E_(c,m) ), indicates that AsH_2 internal excitation accounts for ~64% of the available energy [i.e., hv — D_0(H_2As — H)]. Secondary AsH_2 photodissociation also takes place. Analyses of superimposed structure atop the broad P(E_(c.m)) distribution suggest that AsH_2 is formed with significant a-axis rotation as well as bending excitation. Comparison of the results obtained with AsH_3 versus those of the lighter group-V hydrides (NH_3, PH_3) lends support to the proposed mechanisms. Of the group-V hydrides, AsH3 lies intermediate between the nonrelativistic and relativistic regimes, requiring high-level electronic structure theory.
机译:高n里德伯格飞行时间光谱已用于研究AsH_3的193.3 nm光解。一光子过程的质心平移能量分布为AsH_3 + hv→AsH_2 + H,P(E_(c,m)),表明AsH_2内部激发约占可用能量的64%[即,hv — D_0(H_2As — H)]。次生AsH_2光解离也发生。对宽P(E_(c.m))分布之上的叠加结构的分析表明,AsH_2的形成具有明显的a轴旋转以及弯曲激励。用AsH_3与较轻的V组氢化物(NH_3,PH_3)获得的结果进行比较,为提出的机理提供了支持。在Ⅴ族氢化物中,AsH3位于非相对论和相对论体系之间,需要高级电子结构理论。

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