AI 中文总结
研究自旋轨道选择的Ar+(2P3/2)离子与对/邻-H2分子电荷转移碰撞中的旋转激发，通过量子动力学计算和轨迹表面跳跃分析，发现强吸引相互作用下新的激发机制，产物旋转激发且以前向散射为主，打破硬球假设。
AI 中文摘要
碰撞旋转激发是许多气体环境中的基本过程。教科书上的硬球模型规定，高旋转激发源于正面碰撞，主要导致向后散射，而向前的远程掠射碰撞对旋转能量转移效率低下。本文报道了一个具有强吸引相互作用系统的旋转态分辨产物成像，即自旋轨道选择的Ar+(2P3/2)离子与对/邻-H2分子之间的电荷转移碰撞。令人惊讶的是，H2+产物被旋转激发且以前向散射为主，这与传统观点形成鲜明对比。基于第一性原理非绝热势能矩阵的量子动力学计算重现了这些观测结果。轨迹表面跳跃分析进一步表明，旋转激发大多发生在大碰撞参数下，并且捕获的复合物由于两个碰撞伙伴在分离前的强吸引相互作用而经历轨道运动。这种新机制对于具有强吸引相互作用的碰撞系统应该是普遍的，这打破了硬球假设。
英文摘要
Collisional rotational excitation is a fundamental process in many gaseous environments. The textbook hard-sphere model stipulates that high rotational excitation results from head-on collisions, leading primarily to backward scattering, whereas long-range glancing collisions in the forward direction are inefficient for rotational energy transfer. Here, we report rotational state resolved product imaging for a system with strong attractive interaction, the charge-transfer collision between spin-orbit selected Ar+(2P3/2) ions and para/ortho-H2 molecules. Surprisingly, the H2+ products are rotationally excited and dominated by forward scattering, in sharp contrast to conventional wisdom. Quantum dynamical calculations on a first-principles diabatic potential energy matrix reproduce the observations. Trajectory surface hopping analysis further reveals that rotational excitation occurs mostly with large impact parameters, and the captured complex undergoes orbiting motion owing to the strong attractive interaction between the two collision partners before they break up. This novel mechanism should be general for collisional systems featuring strong attractive interactions, which undermine the hard-sphere assumption.
