Probing the Dependence of Long-Range, Four-Atom Interactions on Intermolecular Orientation. 4. The Dissociation Dynamics of H2/D2···ICl(B,v′=3) and the Observation of Efficient Vibrational–Rotational Energy Transfer
Probing the Dependence of Long-Range, Four-Atom Interactions on Intermolecular Orientation. 4. The Dissociation Dynamics of H2/D2···ICl(B,v′=3) and the Observation of Efficient Vibrational–Rotational Energy Transfer
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探讨长程四原子相互作用对分子间取向的依赖性。
DOI：
10.1021/acs.jpca.2c05817
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Loomis, Richard A.
中科院分区：
文献类型：
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作者：
Darr, Joshua P.;Loomis, Richard A.
研究了不同分子间振动能级下制备的含对氢和邻氢的H2/D2·I35Cl(B,v'=3)配合物的振动预解离动力学。为激发这些配合物的最低能量 T 形能级而测量的 Δv= −1 I35Cl(B,v= 2,j) 旋转产物态分布大多是双峰的。 H2··I35Cl(B,v'=3)配合物的激发测量的旋转分布比D2··I35Cl(B,v'=3)配合物的旋转分布更冷，并且对含氢配合物和邻氢配合物的测量结果之间仅存在轻微差异。离域弯曲水平的激发导致稍微冷的旋转产物状态分布。这些分布表明，动力学结果不仅仅是产物的低能 H2/D2+ I35Cl(B,v= 2) 势表面的内排斥壁的脉冲解离。这些潜力的深度和这些产品可用的能量也有助于动态。 Δv= −2, I35Cl(B,v= 1) 产物通道的形成仅在邻(j= 0)-D2+ I35Cl(B,v'=3) 电势内的能级激发时被识别。该通道的形成是通过 I35Cl(B,v'=3) 振动到 D2 旋转能量转移形成邻(j= 2)-D2+ I35Cl(B,v= 1,j) 产物。
The vibrational predissociation dynamics of H2/D2···I35Cl(B,v′=3) complexes containing bothpara- andortho-hydrogen prepared in different intermolecular vibrational levels were investigated. The Δv= −1 I35Cl(B,v= 2,j) rotational product-state distributions measured for excitation to the lowest-energy T-shaped levels of these complexes are mostly bimodal. The rotational distributions measured for excitation of the H2···I35Cl(B,v′=3) complexes are colder than those of the D2···I35Cl(B,v′=3) complexes, and there are only slight differences between those measured for thepara- andortho-hydrogen containing complexes. Excitation of the delocalized bending levels results in slightly colder rotational product-state distributions. The distributions suggest the dynamics result from more than impulsive dissociation off of the inner repulsive wall of the lower-energy H2/D2+ I35Cl(B,v= 2) potential surfaces of the products. The depths of these potentials and the energies available to these products also contribute to the dynamics. The formation of the Δv= −2, I35Cl(B,v= 1) product channel was only identified for excitation of levels within theortho(j= 0)-D2+ I35Cl(B,v′=3) potential. The formation of this channel occurs via I35Cl(B,v′=3) vibrational to D2rotational energy transfer forming theortho(j= 2)-D2+ I35Cl(B,v= 1,j) products.