NEARLY LINEAR SCALABILITY OF TIME-DEPENDENT DISCRETE VARIABLE REPRESENTATION (TDDVR) METHOD FOR THE DYNAMICS OF MULTI-SURFACE MULTI-MODE HAMILTONIAN

Abstract

Time-Dependent Discrete Variable Representation (TDDVR) method was implemented by involving "classical" trajectories on each degrees of freedom (DOF) for the dynamics of multi-surface multi-mode Hamiltonian. The major focus of this article is to explore the efficiency of the serial and parallelized TDDVR algorithm for relatively large dimensional quantum dynamics in presence of non-adiabaticity among the electronic states. As a model system, the complex photoelectron spectra and non-radiative decay dynamics of trifluoroacetonitrile radical cation ( CF3CN+ ) are theoretically simulated with the aid of such parallelized algorithm, where the five lowest electronic states (X2E, A2A1, B2A2, C2A1, and D2E) of the Hamiltonian are interconnected through several conical intersections in the vicinity of Frank–Condon region with twelve (12) active vibrational modes. The Jahn–Teller splitting of the X2E and D2E states makes the coupled five-surface system to a more challenging quantum dynamical seven-surface twelve-mode model. The results obtained from the TDDVR approach show very good agreement with the profiles of both Multi Configuration Time-Dependent Hartree (MCTDH) methodology and experimental technique, where its' sequencial and parallelized algorithm depict closely linear scalability with the increasing number of basis set vis-a-vis DOFs.