Nonadiabatic excited-state molecular dynamics: On-the-fly limiting of essential excited states
| Autor: | Sergei Tretiak, Sebastian Fernandez-Alberti, Artem Naumov, Tammie Nelson |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: |
POLY-PHENYLENE ETHYNYLENE
General Physics and Astronomy Surface hopping NA-ESMD 010402 general chemistry Kinetic energy 01 natural sciences Molecular dynamics LOCAL KINETIC ENERGY Computational chemistry POLY-PHENYLENE VINYLENE 0103 physical sciences Statistical physics Physical and Theoretical Chemistry Wave function 010304 chemical physics Chemistry Otras Ciencias Químicas Ciencias Químicas Gauge (firearms) 0104 chemical sciences Vibronic coupling Excited state EXCITED STATE LIMITING Relaxation (approximation) FEWEST SWITCHES SURFACE HOPPING CIENCIAS NATURALES Y EXACTAS |
| Popis: | 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. Fil: Nelson, Tammie. Los Alamos National Laboratory; Estados Unidos Fil: Naumov, Artem. Skolkovo Institute Of Science And Technology; Rusia Fil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Tretiak, Sergei. Los Alamos National Laboratory; Estados Unidos |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|