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Vibrational predissociation versus intramolecular vibrational energy redistribution (IVR) in rare gas⋯dihalogen complexes: IVR identified in Ar⋯I2(B, ν′) using velocity-map imaging
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2021-11-16 , DOI: 10.1039/d1cp04727b
Camille Makarem 1 , Jie Wei 1 , Richard A Loomis 1 , Joshua P Darr 2
Affiliation  

The competition between multiple pathways sampled during the energetic relaxation of excited molecules can be difficult to experimentally decipher. The rare gas···dihalogen van der Waals complexes have remained key systems for exploring the competition between relaxation pathways, such as intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP). As these mechanisms can yield the same products, the relaxation pathways traversed are often deduced from the excitation spectra or product-state distributions. In addition to a brief perspective on IVR and VP in rare gas⋯dihalogen complexes, we present new results obtained using time-of-flight velocity-map imaging (VMI) on T-shaped Ar⋯I2(B, ν′, n′ = 0) complexes that illustrate how contributions from these two pathways can be separated. The angular anisotropies of the ion images collected for the I2(B, ν < ν′) fragments indicate the products for certain Ar⋯I2(B, ν′, n′ = 0) levels are weighted along the direction perpendicular to the laser-polarization axis. These distributions are consistent with prompt dissociation of the T-shaped excited-state complexes, likely via direct VP. The distributions measured for other Ar⋯I2(B, ν′, n′ = 0) levels are preferentially along the laser-polarization axis. These initially prepared levels must undergo IVR with nearly resonant Ar⋯I2(B, ν < ν′, n > 0) intermolecular vibrational levels that sample linear Ar–I–I orientations during dissociation.

中文翻译:

稀有气体⋯二卤素复合物中的振动预解离与分子内振动能量再分布 (IVR):使用速度图成像在 Ar⋯I2(B, ν') 中识别的 IVR

在激发分子的能量弛豫期间采样的多个通路之间的竞争可能难以通过实验破译。稀有气体……二卤范德华配合物一直是探索分子内振动能量再分配(IVR)和振动预解离(VP)等弛豫途径之间竞争的关键系统。由于这些机制可以产生相同的产品,因此通常从激发光谱或产品状态分布中推导出所经过的弛豫路径。除了对稀有气体⋯二卤素复合物中的 IVR 和 VP 进行简要介绍外,我们还展示了使用 T 形 Ar⋯I 2 (B, ν ′, n' = 0) 复合物,说明如何分离这两种途径的贡献。为 I 2 (B, ν < ν ') 碎片收集的离子图像的角各向异性表明某些 Ar⋯I 2 (B, ν ', n ' = 0) 能级的乘积沿垂直于激光偏振轴。这些分布与 T 形激发态复合物的迅速解离一致,可能是通过直接 VP。其他 Ar⋯I 2 (B, ν ′, n' = 0) 能级优先沿着激光偏振轴。这些最初准备的能级必须经过 IVR 与几乎共振的 Ar⋯I 2 (B, ν < ν ', n > 0) 分子间振动能级,在解离过程中对线性 Ar–I–I 方向进行采样。
更新日期:2021-11-23
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