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A vector correlation study using a hexapole-oriented molecular beam: photodissociation dynamics of oriented isohaloethane

光解 激发态 化学 原子物理学 交叉分子束 偶极子 光激发 分子束 角动量 激发 分子 分子物理学 物理 光化学 量子力学 有机化学
作者
Dock‐Chil Che,Hiroshi Kawamata,Masaaki Nakamura,Toshio Kasai,King‐Chuen Lin
出处
期刊:Physical Chemistry Chemical Physics [The Royal Society of Chemistry]
卷期号:24 (10): 5914-5920 被引量:2
标识
DOI:10.1039/d1cp05788j
摘要

The photodissociation dynamics of isohaloethane (1-bromo-2-chloro-1,1,2-trifluoroethane) at 234 nm was studied by a sliced imaging technique combined with an oriented molecular beam. The speed and angular distributions of the competitive products of spin-orbit selected Br and Cl atoms were determined by analysis of the obtained images. The anisotropic parameter, β, was found to be 2.0 ± 0.2 for the excited state of Br(2P1/2) (Br*) and 1.2 ± 0.3 for the ground state of Br(2P3/2) (Br). The speed distributions for both Br and Br* exhibited Gaussian-like characteristics. These results indicate that Br atoms were generated by direct formation after excitation through the nσ*(C-Br) potential energy surfaces. In contrast, the angular distributions for the Cl fragments were almost isotropic, while the speed distributions displayed Boltzmann-like characteristics. This suggests that the Cl atoms may form through long-lived parent molecules after photoexcitation. The branching ratio for Br and Cl atom formation was found to be approximately 1.2, that is, Br atom formation occurred preferentially, in contrast to the case of halothane photodissociation reported in our previous work [Che et al., J. Phys. Chem. A, 2020, 124, 5288]. A vector correlation study between the laser polarization axis and the direction of the dipole moment revealed a similar tendency for all photofragments, suggesting that the fragments were formed through a common excited state of isohaloethane. The vector correlation was also studied theoretically for comparison with the experimental results. The angle between the transition dipole moment in photodissociation and the permanent dipole moment was found to be 42 ± 15°. The obtained results indicate that this vector correlation approach combined with an oriented molecular beam is a powerful tool for determining the transition dipole moments in photodissociation.
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