Strong geometric-phase effects in the hydrogen-exchange reaction at high collision energies
Strong geometric-phase effects in the hydrogen-exchange reaction at high collision energies
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DOI：
10.1063/1.2897920
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发表时间：
2008-03-28
影响因子：
4.4
通讯作者：
Ruiz, Daniel Pelaez
中科院分区：
文献类型：
--
作者：
Bouakline, Foudhil;Althorpe, Stuart C.;Ruiz, Daniel Pelaez
我们报道了H+H-2(nu(0)=0，j(0)=0)->；H-2(nu，j)+H反应的态与态反应几率和截面的量子波包计算，总能量高于基态势能最小值4.5 eV。使用Mahapatra等人的非绝热势能方法重复计算：(I)仅使用基态，(Ii)基态加上斜线非Born-Oppenheimer修正，(Iii)基态，斜线非Born-Oppenheimer修正和几何相(GP)，以及(Iv)包括所有非绝热耦合的两个电子态。作者声明：[J.Phys.化学。A 105,2321(2001)]。计算(III)和(IV)的结果非常接近，表明高电子态对态-态动力学的贡献很小，即使在能量远高于锥形交点极小值(2.74 eV)的情况下也是如此。在总能量高于3.5 eV时，许多态对态反应几率都表现出很强的GP效应，表明它们主要受单过渡态和双过渡态(1-TS和2-TS)反应路径的干扰。这些效应经受住了部分波的相干求和，在状态到状态的微分截面中产生了特征，这些特征可以在角度分辨率类似于20度的实验中检测到。1-TS和2-TS贡献之间干扰的有效去相导致积分截面中的GP几乎完全消除，从而延续了在早期工作中在较低能量下观察到的趋势。(C)2008年美国物理研究所。
We report quantum wave packet calculations of state-to-state reaction probabilities and cross sections for the reaction H + H-2(nu(0)= 0, j(0)= 0) -> H-2 (nu, j) + H, at total energies up to 4.5 eV above the ground state potential minimum. The calculations are repeated using (i) the ground electronic state only, (ii) the ground state plus the diagonal non-Born-Oppenheimer correction, (iii) the ground state, diagonal non-Born-Oppenheimer correction and geometric phase (GP), and (iv) both electronic states including all nonadiabatic couplings, using the diabatic potential approach of Mahapatra et al. [J. Phys. Chem. A 105, 2321 (2001)]. The results for calculations (iii) and (iv) are in very close agreement, showing that the upper electronic state makes only a very small contribution to the state-to-state dynamics, even at energies much higher than the conical intersection minimum (at 2.74 eV). At total energies above 3.5 eV, many of the state-to-state reaction probabilities show strong GP effects, indicating that they are dominated by interference between one-and two-transition-state (1-TS and 2-TS) reaction paths. These effects survive the coherent sum over partial waves to produce features in the state-to-state differential cross sections which could be detected in an experiment with an angular resolution of similar to 20 degrees. Efficient dephasing of the interference between the 1-TS and 2-TS contributions causes almost complete cancellation of the GP in the integral cross sections, thus continuing a trend observed at lower energies in earlier work. (C) 2008 American Institute of Physics.