Effects of vibrational excitation on the F + H(2)O → HF + OH reaction: dissociative photodetachment of overtone-excited [F-H-OH]().
Effects of vibrational excitation on the F + H(2)O → HF + OH reaction: dissociative photodetachment of overtone-excited [F-H-OH]().
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振动激发对 F H2O -> HF 加 OH 反应的影响：泛音激发 [F-H-OH](-) 的解离光脱离
DOI：
10.1039/c7sc03364h
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发表时间：
2017-11-01
期刊：
影响因子：
8.4
通讯作者：
Continetti RE
中科院分区：
文献类型：
--
作者：
Ray AW;Ma J;Otto R;Li J;Guo H;Continetti RE
光分离振动激发的FH2O -将能量通道到F + H2O反应的反应坐标中，如本实验-理论联合研究所示。反应F + H2O→HF + OH是一个四原子体系，为反应动力学提供了重要的基准。在这个反应的过渡态氢原子的转移预计表现出强烈的依赖于反应物的振动激发。在本研究中，利用光电子-光电碎片重合（PPC）光谱研究了振动激发的F - (H2O)前体阴离子的光剥离效应，并与从头算势能面上的全六维量子动力学计算进行了比较。在hν UV = 4.80 eV光剥离之前，用可调谐红外激光激发了前驱体F - (H2O)中离子氢键模式的泛音，2ν IHB在2885 cm-1处。实验和理论均表明，在Franck-Condon光剥离作用下，阴离子中的振动能量可被光电子有效地带走，同时也表明了向F + H2O反应通道分支增加的证据。实验结果表明，产物旋转激励的作用大于理论。改进的势能面和较长的波包传播时间将有助于进一步研究这种差异的性质。
Photodetaching vibrationally excited FH2O– channels energy into the reaction coordinate of the F + H2O reaction, as shown in this joint experimental-theoretical study. The reaction F + H2O → HF + OH is a four-atom system that provides an important benchmark for reaction dynamics. Hydrogen atom transfer at the transition state for this reaction is expected to exhibit a strong dependence on reactant vibrational excitation. In the present study, the vibrational effects are examined by photodetachment of vibrationally excited F–(H2O) precursor anions using photoelectron-photofragment coincidence (PPC) spectroscopy and compared with full six-dimensional quantum dynamical calculations on ab initio potential energy surfaces. Prior to photodetachment at hν UV = 4.80 eV, the overtone of the ionic hydrogen bond mode in the precursor F–(H2O), 2ν IHB at 2885 cm–1, was excited using a tunable IR laser. Experiment and theory show that vibrational energy in the anion can be effectively carried away by the photoelectron upon a Franck–Condon photodetachment, and also show evidence for an increase of branching into the F + H2O reactant channel. The experimental results suggest a greater role for product rotational excitation than theory. Improved potential energy surfaces and longer wavepacket propagation times would be helpful to further examine the nature of the discrepancy.
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影响因子：
4.4
作者：
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通讯作者：
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