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The effect of phonon modes and electron-hole pair (elhp) couplings at different surface temperature on 2(v = 0, 1; j = 0)-(111) collision has been explored by assuming weakly correlated interactions between molecular Degrees of Freedoms (DOFs) with surface modes and elhp excitations through a Hartree product type wavefunction, where the initial state distributions for the phonon modes and the elhp couplings are incorporated by using Bose-Einstein and Fermi-Dirac probability factors, respectively. We carry out four (4D⊗2D)- and six (6D)- dimensional quantum dynamics on such an effective Hamiltonian, and depict the calculated sticking/transition probabilities and energy transfer from molecule to the surface. The phonon modes slightly affect the sticking probability by broadening the profile, but the transition probability are substantially changed with respect to the rigid surface. On the contrary, the inclusion of elhp coupling along with phonon modes does not change the results much compared to the only phonon case. We formulate an effective Hamiltonian for D2 ( v = 0, 1; j = 0)-Cu(111) collision processes from first principle to include the surface temperature through phonon modes and electron-hole pair couplings, where the barrier (ttb, bth) heights of the potential undergo change substantially both with respect to time and temperature, and become responsible for the broadening of sticking probability and modifying the transition probability. The figure shows as the collision energy increases, the transition probability attends a saturation as predicted by experimental observation. For the system D2 ( v = 0, 1; j = 0)-Cu(111), the major contribution due to surface temperature arises from phonon modes, where the electron-hole pair coupling has minor effect on calculated probabilities as obtained by other contemporary theoretical calculations. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]