Pino Ilaria, Martinazzo Rocco, Tantardini Gian Franco
Dipartimento di Chimica, Università Federico II, Complesso Monte S. Angelo, via Cintia, 80126, Napoli, Italy.
Phys Chem Chem Phys. 2008 Sep 28;10(36):5545-51. doi: 10.1039/b805750h. Epub 2008 Jul 23.
Quasi-classical trajectory calculations have been performed on the adiabatically allowed reactions taking place on the two lowest-lying electronic states of the LiH2+ system, using the ab initio potential energy surfaces of Martinazzo et al. (J. Chem. Phys., 2003, 119, 11 241). These reactions comprise: (i) the exoergic H2 and H2+ formation occurring through LiH+ + H and LiH + H+ collisions in the ground and in the first electronically excited state, respectively; (ii) the endoergic (ground state) LiH+ dissociation induced by collisions with H atoms; and (iii) the endoergic (excited state) Li + H2+ --> LiH + H+ reaction. The topic is of relevance for a better understanding of the lithium chemistry in the early universe. Thermal rate constants for the above reactions have been computed in the temperature range 10-5000 K and found in reasonably good agreement with estimates based on the capture model.
利用Martinazzo等人（《化学物理杂志》，2003年，第119卷，第11241页）的从头算势能面，对LiH₂⁺体系两个最低电子态上发生的绝热允许反应进行了准经典轨迹计算。这些反应包括：（i）分别通过基态和第一电子激发态下的LiH⁺ + H和LiH + H⁺碰撞产生的放热H₂和H₂⁺形成；（ii）与H原子碰撞诱导的吸热（基态）LiH⁺解离；以及（iii）吸热（激发态）Li + H₂⁺→LiH + H⁺反应。该主题对于更好地理解早期宇宙中的锂化学具有重要意义。已在10 - 5000 K的温度范围内计算了上述反应的热速率常数，发现与基于捕获模型的估计结果相当吻合。
