Quasi-Bound States of the F·CH4 Complex.
Quasi-Bound States of the F·CH4 Complex.
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DOI：
10.1021/acs.jpca.5b11694
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发表时间：
2016-01
期刊：
影响因子：
--
通讯作者：
D. Schäpers;U. Manthe
中科院分区：
文献类型：
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作者：
D. Schäpers;U. Manthe
F+CH_4→HF+CH_3反应是一个被广泛研究的具有早期过渡态的多原子反应的典型例子。预活性络合物被认为在反应动力学中起着重要作用。本文详细研究了亚稳F·CH4络合物形成的长寿命共振态。采用多组态含时Hartree方法和单个绝热势能面的全维量子动力学计算方法，研究了总角动量为零的F·CH4络合物的低位准束缚态.计算得到F·CH4络合物相对于反应物渐近线的解离能为170 cm(-1)。发现了约60个能量低于反应物渐近线的共振态。对计算的低位态波函数的详细分析表明，F和CH4的相对旋转几乎是自由的，F-CH4的伸缩振动几乎是可分离的。本文的结果与研究CH4F(-)阴离子的光脱离谱的过渡态光谱实验进行了比较。
The F + CH4 → HF + CH3 reaction is an intensively studied prototypical example of a polyatomic reaction showing an early transition state. Prereactive complexes are assumed to play an important role in the dynamics of the reaction. In this work, the long-living resonance states resulting from the formation of a metastable F·CH4 complex are investigated in detail. Full-dimensional quantum dynamics calculations employing the multiconfigurational time-dependent Hartree (MCTDH) approach and a single adiabatic potential energy surface are used to study the low-lying quasi-bound states of the F·CH4 complex for vanishing total (nuclear) angular momentum. The computed dissociation energy of the F·CH4 complex with respect to the reactant asymptote is 170 cm(-1). About 60 resonance states with energies below the reactant asymptote are found. A detailed analysis of the computed wave function of the low-lying states shows an almost free relative rotation of F and CH4 and an approximately separable F-CH4 stretching vibration. The present results are compared with transition state spectroscopy experiments which study the photodetachment spectrum of the CH4F(-) anion.