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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Simulations of ICl-(CO2)n Photodissociation: Effects of Structure, Excited State Charge Flow, and Solvent Dynamics
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Simulations of ICl-(CO2)n Photodissociation: Effects of Structure, Excited State Charge Flow, and Solvent Dynamics

机译：ICl-（CO2）n光解离的模拟：结构，激发态电荷流和溶剂动力学的影响

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Experiments on the photodissociation of ICl- within size-selected CO2 clusters [Nadal, M. E.; Kleiber, P. D.;Lineberger, W. C. J. Chem. Phys. 1996, 105, 504.] differ from analogous experiments on homonuclear systems in two major ways: an early onset of caged, ICl--based products with cluster size peaking at n ) 5 and a rapid decline of caging after n ) 5 in favor of dissociated, Cl--based fragments. Using an effective Hamiltonian model for the solute electronic structure and nonadiabatic MD trajectories, we have simulated the photodissociation of these clusters and found good agreement between experimental and simulated product distributions. The strong preference of the solvent for chlorine in the initial cluster structure, along with favorable kinematics, leads to the efficient caging at small n. At all cluster sizes, the Cl--based fragments are formed by an adiabatic process and are accompanied by spin-orbit excited iodine. Caging of ICl- also occurs on the excited state potential surface, and electronic relaxation is not observed during the 100 ps trajectories.For n > 5, the initially caged products appear to be metastable, decaying to solvent-separated Cl I pairs that subsequently dissociate, leading to the falloff in the caging fraction in the larger clusters
机译：在大小选择的CO2团簇中ICl-的光解离实验[Nadal，M. E .; Kleiber，P.D .; Lineberger，W.C. J. Chem。物理[1996，105，504.]与同核系统的类似实验有两个主要方面的区别：笼状，基于ICl的产品的早期发作，簇大小在n）5达到峰值，而在n）5以后笼养迅速下降，有利于分离的基于Cl的碎片使用有效的汉密尔顿模型用于溶质电子结构和非绝热MD轨迹，我们已经模拟了这些团簇的光解离，并发现了实验和模拟产品分布之间的良好一致性。初始簇结构中溶剂对氯的强烈偏爱，以及良好的运动学特性，导致在n较小时有效的笼蔽。在所有簇尺寸下，基于Cl的碎片都是通过绝热过程形成的，并伴有自旋轨道激发的碘。 ICl-的笼统也发生在激发态势能表面上，并且在100 ps的轨迹中没有观察到电子弛豫。对于n> 5，最初笼中的产物似乎是亚稳态的，衰变为溶剂分离的Cl I对，随后解离。 ，导致较大群集中的笼子比例下降

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