Wave packet study of the UV photodissociation of the Ar2HBr complex

Abstract

The photodissociation dynamics of the Ar2HBr van der Waals molecule is studied using the multiconfiguration time-dependent Hartree method. Standard Jacobian coordinates are used to describe the molecule. Two four-dimensional calculations are carried out where the rotation of the Ar2 molecule and, in addition, either the vibration of Ar2-Br or that of Ar2 are frozen. The time-evolution of the probability density in the different modes and the calculation of the dissociative flux show that the dissociating hydrogen atom preferentially moves out of the plane defined by Ar2 and Br. A comprehensive study of the cage effect in the process is presented.

Quantum and classical non-adiabatic dynamics of Li$_{2}^{+}$Ne photodissociation

“…This is typically the case for photodissociation processes where the wavepacket must eventually be propagated to large values of the scattering coordinates and for which an exact quantum wavepacket calculation becomes rapidly impracticable. MCTDH has been successfully applied to various photodissociation processes [6,[12][13][14][15][16][17][18][19][20][21][22][23][24][25] and to multimode nonadiabatic dynamics [26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42]. In this work, we also establish a link with previous studies [4,43,44] by performing a simulation by means of classical molecular dynamics with trajectory surface hopping (TSH) approach [45][46][47].…”

Quantum Dynamical Approach to Ultrafast Molecular Desorption from Surfaces

“…This study is in line with earlier theoretical − and experimental work , on the photodissociation of hydrogen halides on (ionic) insulators. It aims at a better understanding of surface-aligned chemistry, on the unravelling of differences to the well-studied dissociation of HCl in the gas phase, van der Waals complexes (e.g., Ar−HCl , or Ar 2 −HBr), and in matrices (e.g., in solid Ar), and on practical aspects of pollution chemistry.…”

Exact and constrained kinetic energy operators for polyatomic molecules: The polyspherical approach

“…The KEO of Eq. (138) was also applied to the study of the photo-dissociation dynamics of the Ar 2 HBr van der Waals molecule with MCTDH [133]. Obviously, the reduced masses are different for Ar 2 HBr (see Ref.…”

“…Obviously, the reduced masses are different for Ar 2 HBr (see Ref. [133] for their actual values). In addition, it goes without saying that the KEO of Eq.…”