Surface hopping dynamics in periodic solid-state materials with a linear vibronic coupling model

Abstract

We report a surface hopping approach in which the implemented linear vibronic coupling Hamiltonian is constructed and the electronic wavefunction is propagated in the reciprocal space. The parameters of the linear vibronic coupling model, including onsite energies, phonon frequencies, and electron-phonon couplings, are calculated with density-functional theory and density-functional perturbation theory, and interpolated in fine sampling points of the Brillouin zone with maximally localized Wannier functions. Using this approach, we studied the relaxation dynamics of the photo-excited hot carrier in a one-dimensional periodic carbon chain. The results show that the completeness of the number of Hilbert space k-points and the number of phonon q-points play important roles in the hot carrier relaxation processes. By calculating the relaxation times of hot carriers under different reciprocal space sampling and extrapolating with the stretched-compressed exponential function, the relaxation times of hot electrons and holes in the quasi-continuous energy band are obtained. By considering the feedback effect in the hopping processes and analyzing the time-dependent phonon energy in different normal modes, we found that the long-wave longitudinal optical phonons play a major role in the relaxation dynamics of hot electrons and holes. We therefore provided herein an efficient and accurate approach for modeling the photophysical processes in periodic solid-state material systems.

Mixed Quantum–Classical Dynamics under Arbitrary Unitary Basis Transformations

“…In a followup work, henceforth referred to as Paper II, 23 we have extended reciprocal-space MQC dynamics for the popular fewest-switches surface hopping (FSSH) method. 24 Since then, reciprocal-space MQC dynamics has been combined with density-functional theory and density-functional perturbation theory, 25 and has found application in the modeling of the Floquet nonadiabatic dynamics of laser-dressed solid-state materials 26 as well as the modeling of optical line widths in monolayer transition-metal dichalcogenides. 27 While reciprocal-space MQC dynamics is particularly effective in describing band-like phenomena, its effectiveness deteriorates once the periodicity of the crystal lattice becomes disrupted, and lattice momentum is no longer a good quantum number.…”

“…In a follow-up work, henceforth referred to as Paper II, we have extended reciprocal-space MQC dynamics for the popular fewest-switches surface hopping (FSSH) method . Since then, reciprocal-space MQC dynamics has been combined with density-functional theory and density-functional perturbation theory, and has found application in the modeling of the Floquet nonadiabatic dynamics of laser-dressed solid-state materials as well as the modeling of optical line widths in monolayer transition-metal dichalcogenides …”