Non-adiabatic effects in F + CHD3 reactive scattering.
Non-adiabatic effects in F + CHD3 reactive scattering.
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DOI：
10.1063/1.4984593
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发表时间：
2017-06
期刊：
影响因子：
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通讯作者：
J. Palma;U. Manthe
中科院分区：
文献类型：
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作者：
J. Palma;U. Manthe
研究了非绝热跃迁对F（2 P）+CHD 3（ν1）→ DF + CHD 2和F（2 P）+CHD 3（ν1）→ HF + CD 3反应的影响.利用轨道表面跳跃和振动与自旋轨道耦合的非绝热势能矩阵模拟了原子核的动力学。为了便于计算，Tully的最少切换算法适用于使用复杂的非绝热势能矩阵。对于CHD 3与基态氟原子F（2 P3/2）的反应，发现先前计算的绝热截面与非绝热截面之间的比率在1.4至2.1的范围内。实际比率取决于CHD 3的平移能和初始振动状态。发现CHD 3（ν1 = 1）的总反应性总是大于CHD 3（ν1=0）的总反应性，这主要是因为HF + CD 3通道的截面增加。因此，在理论处理中包括非绝热转变不能解决理论和实验之间存在的分歧。发现CHD 3与自旋轨道激发的氟原子F（2 P1/2）反应的截面明显小于与F（2 P3/2）反应的截面。
The effect of non-adiabatic transitions on the F(2P) + CHD3(ν1) → DF + CHD2 and F(2P) + CHD3(ν1) → HF + CD3 reactions is investigated. The dynamics of the nuclei was simulated using trajectory surface hopping and a vibronically and spin-orbit coupled diabatic potential energy matrix. To facilitate the calculations, the fewest switching algorithm of Tully was adapted to the use of a complex diabatic potential energy matrix. For reactions of CHD3 with ground state fluorine atoms, F(2P3/2), the ratio between the previously computed adiabatic cross sections and the non-adiabatic ones was found to range from 1.4 to 2.1. The actual ratio depends on the translational energy and the initial vibrational state of CHD3. The total reactivity of CHD3(ν1 = 1) was found to be always larger than that of CHD3(ν1=0) mainly because of the increase in the cross sections for the HF + CD3 channel. Thus, the inclusion of non-adiabatic transitions in the theoretical treatment cannot resolve the existing disagreement between theory and experiment. Cross sections for the reaction of CHD3 with spin-orbit excited fluorine atoms, F(2P1/2), were found to be significantly smaller than the ones for reaction with F(2P3/2).