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研究分子的碎裂机制以及碎片的动能分布，有助于理解其在等离子体物理、生物组织的辐射损伤和星际化学等方面的重要作用。本文利用冷靶反冲离子动量谱仪开展了3 keV/u的Ar8+离子束与氟甲烷气体分子束的碰撞实验，聚焦CH3F3+离子C-F键和C-H键断裂后形成H++CH2++F+这一三体碎裂通道，测得三个碎片离子的三维动量。借助离子-离子动能谱、Newton图和Dalitz图展示碎片的动能与动量关联，分析了H++CH2++F+通道的解离机制。研究发现，该通道存在协同碎裂以及通过中间体CH2F2+顺序碎裂两种解离方式，其中协同碎裂占主导地位。此外，实验上观测到两种不同动力学特征的协同碎裂过程，表明CH3F3+离子中H原子可以具有不同的化学环境，这可能是由于分子异构化产生不同分子构型或者Jahn-Teller效应使得分子产生不同C-H键所致。Investigating molecular fragmentation mechanisms and the kinetic energy distributions of fragments provides crucial insights into their roles in plasma physics, radiation-induced damage in biological tissues, and interstellar chemistry. In this study, we conducted collision experiments between 3 keV/u Ar8+ ions and CH3F molecules using a cold target recoil ion momentum spectrometer. We focused on the three-body fragmentation channel H+ + CH2+ + F+ resulting from C-F and C-H bond cleavage in CH3F3+ ions, and measured the three-dimensional momentum vectors of all fragment ions. The fragmentation mechanism involved was analyzed using ion-ion kinetic energy correlation spectra, Newton diagrams, Dalitz plots and other correlation spectra.
Our results reveal two distinct dissociation mechanisms for the H+ + CH2+ + F+ channel, i.e., concerted and sequential fragmentation, with the former one being dominant. In the sequential fragmentation process, H+ and the intermediate CH2F2+ are firstly formed, followed by further fragmentation of the intermediates into CH2+ and F+. No sequential pathways involving HF2+ or CH32+ intermediates were identified. Furthermore, we observed two types of concerted fragmentation processes with different dynamical characteristics, suggesting that hydrogen atoms in CH3F3+ may occupy different chemical environments. This phenomenon could originate from either molecular isomerization producing different structural geometries or the Jahn-Teller effect leading to inequivalent C-H bonds. This study reveals the three-body dissociation dynamics of CH3F3+ induced by highly charged ion collisions, highlighting the significant role of the Jahn-Teller effect or molecular isomerization in the ionic dissociation of polyatomic molecules.-
Keywords:
- fluoromethane /
- dissociative ionization /
- three-body fragmentation /
- COLTRIMS
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