Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2025

A Density Functional Theory and Semiempirical Framework for Trajectory Surface Hopping on Extended Systems

Jan-Robert Vogt
  • Fonction : Auteur
Michael Schulz
  • Fonction : Auteur
Maurizio Persico
Giovanni Granucci
Jürg Hutter
  • Fonction : Auteur
Anna Hehn

Résumé

Nonadiabatic molecular dynamics simulations provide a theoretical understanding of various excited-state processes in photochemistry, offering access to band widths, radiative or nonradiative relaxation and corresponding lifetimes, excited-state energies, and charge transfer. The range of method developments within the framework of time-dependent density functional theory is exceedingly large for molecular quantum chemistry. Still, it shrinks significantly when aiming to treat periodic boundary conditions. To address this gap and complement existing software packages for solid-state nonadiabatic molecular dynamics, we present an interface between the CP2K electronic structure and the NEWTON-X surface hopping codes. The interface features the generation of initial conditions, as well as adiabatic and nonadiabatic molecular dynamics, based on phenomenological or numerical time-derivative couplings. Setups are validated on gas-phase pyrazine, with electronic absorption spectra and excited-state populations for transitions between the lowest singlet states being in agreement with established molecular quantum chemistry methods. Extending the system size to crystalline pyrazine, limitations of approximate couplings are discussed, and the efficiency and applicability of the interface are demonstrated by computing broad spectra over several eV and 100 fs trajectories, considering couplings between all 80th lowest excited states, at low computational cost with a mixed semiempirical density functional theory setup.

Fichier principal
Vignette du fichier
p206_vogt_cp2k-nx_jctc_2025.pdf (3.95 Mo) Télécharger le fichier
Origine Publication financée par une institution
Licence

Dates et versions

hal-05321933 , version 1 (20-10-2025)

Licence

Identifiants

Citer

Jan-Robert Vogt, Michael Schulz, Rafael Souza Mattos, Mario Barbatti, Maurizio Persico, et al.. A Density Functional Theory and Semiempirical Framework for Trajectory Surface Hopping on Extended Systems. Journal of Chemical Theory and Computation, 2025, ⟨10.1021/acs.jctc.5c01082⟩. ⟨hal-05321933⟩
45 Consultations
124 Téléchargements

Altmetric

Partager

  • More