Perera Chatura, Ross Ethan, Zou Junxiang, Guo Hua, Suits Arthur G
Department of Chemistry, University of Missouri, Columbia, Missouri 65211, United States.
Department of Chemistry and Chemical Biology, Center for Computational Chemistry, University of New Mexico, Albuquerque, New Mexico 87131, United States.
J Phys Chem A. 2024 Dec 12;128(49):10516-10524. doi: 10.1021/acs.jpca.4c05742. Epub 2024 Nov 27.
State-to-state spin-orbit changing collisions of vibrationally excited nitric oxide (NO) with argon (Ar) were studied across a wide collision energy range from 3.5 to 11,200 cm (0.43 meV to 1.4 eV) using two molecular beam geometries. Stimulated emission pumping (SEP) for precise initial state preparation and velocity map imaging (VMI) for detailed scattering image capture were employed. These methods enable the study of quantum-state-resolved differential cross sections (DCSs) and provide comprehensive insight into the collision dynamics over both quantum and classical regimes. Theoretical predictions using quantum mechanical close-coupling (QMCC) calculations based on high-level coupled cluster (CCSD(T)) and multireference configuration interaction (MRCI) potential energy surfaces (PESs) are compared with experimental results enabling the testing of both repulsive and attractive parts of the PESs. This study highlights the challenges in accurately modeling spin-orbit changing collisions and underscores the importance of precise experimental data for validating theoretical models, thereby advancing our understanding of nonadiabatic collision dynamics.
利用两种分子束几何结构,在3.5至11200厘米(0.43毫电子伏特至1.4电子伏特)的宽碰撞能量范围内,研究了振动激发的一氧化氮(NO)与氩(Ar)之间的态间自旋轨道变化碰撞。采用了受激辐射泵浦(SEP)进行精确的初始态制备,以及速度映射成像(VMI)进行详细的散射图像捕获。这些方法能够研究量子态分辨的微分截面(DCSs),并全面洞察量子和经典区域的碰撞动力学。基于高级耦合簇(CCSD(T))和多参考组态相互作用(MRCI)势能面(PESs)的量子力学紧密耦合(QMCC)计算的理论预测与实验结果进行了比较,从而能够测试PESs的排斥和吸引部分。这项研究突出了精确模拟自旋轨道变化碰撞的挑战,并强调了精确实验数据对验证理论模型的重要性,从而推进了我们对非绝热碰撞动力学的理解。