Dashevskaya E I, Litvin I, Nikitin E E, Troe J
Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel.
Institut für Physikalische Chemie, Universität Göttingen, Tammannstrasse 6, D-37077 Göttingen, Germany.
J Chem Phys. 2016 Dec 28;145(24):244315. doi: 10.1063/1.4972129.
Rate coefficients for capture of H(j = 0,1) by H are calculated in perturbed rotor approximation, i.e., at collision energies considerably lower than Bhc (where B denotes the rotational constant of H). The results are compared with the results from an axially nonadiabatic channel (ANC) approach, the latter providing a very good approximation from the low-temperature Bethe-Wigner to the high temperature Langevin limit. The classical ANC approximation performs satisfactorily at temperatures above 0.1 K. At 0.1 K, the rate coefficient for j=1 is about 25% higher than that for j = 0 while the latter is close to the Langevin rate coefficient. The Bethe-Wigner limit of the rate coefficient for j = 1 is about twice that for j = 0. The analysis of the relocking of the intrinsic angular momentum of H during the course of the collision illustrates the significance of relocking in capture dynamics in general.
通过微扰转子近似法计算了H对H(j = 0,1)的俘获速率系数,即在碰撞能量远低于Bhc(其中B表示H的转动常数)的情况下进行计算。将结果与轴向非绝热通道(ANC)方法的结果进行了比较,后者从低温的贝特 - 维格纳极限到高温的朗之万极限都提供了非常好的近似。经典的ANC近似在高于0.1 K的温度下表现令人满意。在0.1 K时,j = 1的速率系数比j = 0的速率系数高约25%,而后者接近朗之万速率系数。j = 1的速率系数的贝特 - 维格纳极限约为j = 0的两倍。对碰撞过程中H的内禀角动量重新锁定的分析说明了重新锁定在俘获动力学中的一般重要性。