Artículos de revistas
Nonadiabatic excited-state molecular dynamics: On-the-fly limiting of essential excited states
Fecha
2016-12Registro en:
Nelson, Tammie; Naumov, Artem; Fernández Alberti, Sebastián; Tretiak, Sergei; Nonadiabatic excited-state molecular dynamics: On-the-fly limiting of essential excited states; Elsevier Science; Chemical Physics; 481; 12-2016; 84-90
0301-0104
CONICET Digital
CONICET
Autor
Nelson, Tammie
Naumov, Artem
Fernández Alberti, Sebastián
Tretiak, Sergei
Resumen
The simulation of nonadiabatic dynamics in extended molecular systems involving hundreds of atoms and large densities of states is particularly challenging. Nonadiabatic coupling terms (NACTs) represent a significant numerical bottleneck in surface hopping approaches. Rather than using unreliable NACT cutting schemes, here we develop “on-the-fly” state limiting methods to eliminate states that are no longer essential for the non-radiative relaxation dynamics as a trajectory proceeds. We propose a state number criteria and an energy-based state limit. The latter is more physically relevant by requiring a user-imposed energy threshold. For this purpose, we introduce a local kinetic energy gauge by summing contributions from atoms within the spatial localization of the electronic wavefunction to define the energy available for upward hops. The proposed state limiting schemes are implemented within the nonadiabatic excited-state molecular dynamics framework to simulate photoinduced relaxation in poly-phenylene vinylene (PPV) and branched poly-phenylene ethynylene (PPE) oligomers for benchmark evaluation.