Quasiclassical dynamics of the I2–Ne2 vibrational predissociation: A comparison with experiment

Abstract

Oneatom cage effect in collinear I2(B)-Ar complexes: A timedependent wave packet study J. Chem. Phys. 105, 9072 (1996) The vibrational predissociation dynamics of the I 2 (B,v) -Ne 2 complex is investigated for several vibrational levels of I 2 , using a quasiclassical trajectory approach. The time evolution of the population of nascent I 2 fragments is calculated. A model is proposed which reproduces the results of the classical trajectories, and allows to obtain the lifetimes associated with the dissociation of the two van der Waals ͑vdW͒ bonds. The classical lifetimes are higher in general than the experimental ones of Zewail and co-workers ͓J. Chem. Phys. 97, 8048 ͑1992͔͒. The classical method appears to overestimate mechanisms of energy redistribution between the modes, which slow down the dissociation of the cluster. However, the behavior of the lifetimes with the initial iodine vibrational excitation is in very good agreement with experiment. A sequential path of fragmentation of the two weak bonds via direct predissociation is found to dominate, producing I 2 ͑B,v -2͒ϩ2Ne fragments. Although with smaller probability, alternative dissociation paths are observed involving statistical mechanisms of internal energy redistribution. In these paths, the energy initially transferred by the iodine heats the vdW modes without breaking the complex. Further energy transfer produces either simultaneous or sequential dissociation of the two weak bonds in a rather evaporative way, populating the v -2 and v -3 exit channels.

Dynamics of structural relaxation upon Rydberg excitation of an NO impurity in rare gas solid matrices

“…The Ne-Ne, Ar -Ar, Kr-Kr, and Xe-Xe, interaction potentials were taken from the literature [15,16]. For the ground state, NO(X [17].…”

An ab initio study of Xe–NO(X2II) and Xe–NO(A2Σ+) potential energy surfaces

“…These studies have used isotropic potentials for the NO(X 2 )-RG interactions from the experimental results of Thuis et al [47] for RG = Ar, Kr, Xe and from reference [48] for RG = Ne. However, for the NO(A 2 + )-RG (RG = Ne, Kr, Xe) interactions, several theoretical approaches have been used.…”

Full-dimensional quantum study of the vibrational predissociation of the I2⋯Ne2 cluster

“…While the three-atom systems have been studied extensively using a full quantum treatment, the four-atom system is, up to now, treated either quantum mechanically in reduced dimensionality [10][11][12][13][14][15][16] or using quasiclassical trajectories. [17][18][19][20] Another approach combined a quasiclassical treatment of the four-atom complex followed by a quantum treatment of the three-atom complex once the first rare gas atom has dissociated. 21 Due to the weakness of the interaction, already one vibrational quanta transferred to the van der Waals modes is sufficient to dissociate one rare gas atom.…”