info:eu-repo/semantics/article
Nonadiabatic Excited-State Molecular dynamics methodologies: Comparison and convergence
Fecha
2021-03Registro en:
Freixas Lemus, Victor Manuel; White, Alexander J.; Nelson, Tammie; Song, Huajing; Makhov, Dmitry V.; et al.; Nonadiabatic Excited-State Molecular dynamics methodologies: Comparison and convergence; American Chemical Society; Journal of Physical Chemistry Letters; 12; 11; 3-2021; 2970-2982
1948-7185
CONICET Digital
CONICET
Autor
Freixas Lemus, Victor Manuel
White, Alexander J.
Nelson, Tammie
Song, Huajing
Makhov, Dmitry V.
Shalashilin, Dmitrii
Fernández Alberti, Sebastián
Tretiak, Sergei
Resumen
Direct atomistic simulation of nonadiabatic molecular dynamics is a challenging goal that allows important insights into fundamental physical phenomena. A variety of frameworks, ranging from fully quantum treatment of nuclei to semiclassical and mixed quantum-classical approaches, were developed. These algorithms are then coupled to specific electronic structure techniques. Such diversity and lack of standardized implementation make it difficult to compare the performance of different methodologies when treating realistic systems. Here, we compare three popular methods for large chromophores: Ehrenfest, surface hopping, and multiconfigurational Ehrenfest with ab initio multiple cloning (MCE-AIMC). These approaches are implemented in the NEXMD software, which features a common computational chemistry model. The resulting comparisons reveal the method performance for population relaxation and coherent vibronic dynamics. Finally, we study the numerical convergence of MCE-AIMC algorithms by considering the number of trajectories, cloning thresholds, and Gaussian wavepacket width. Our results provide helpful reference data for selecting an optimal methodology for simulating excited-state molecular dynamics.