Surface Hopping Dynamics on Adiabatic States Propagated with Real-Time TDDFT

Abstract

Real-time time-dependent density functional theory (RT-TDDFT) is widely used to simulate ultrafast electron dynamics, but it is usually coupled to the nuclei through the mean-field Ehrenfest approximation, which cannot describe wavepacket branching and violates detailed balance. Surface hopping avoids these problems, but has not previously been combined with RT-TDDFT because real-time propagation does not directly provide the necessary adiabatic states. In this work we introduce an energy-scaled time-dependent Kohn--Sham (TDKS) propagation scheme, motivated by the quantum adiabatic theorem. Scaling widens the separation between electronic and nuclear timescales, so that each propagated state follows the adiabatic surface selected by its initial condition: either the ground state or a non-Aufbau self-consistent-field (ΔSCF) solution. The propagation thereby avoids the convergence failures of static SCF solvers in regions of strong nonadiabatic coupling. Because the independently propagated states are complex-valued and not mutually orthogonal, we reformulate the mapping approach to surface hopping (MASH) in a complex adiabatic basis and introduce a dynamical transition orbital (DTO) gauge that restores a well-defined particle--hole representation for evaluating time-derivative couplings and nonadiabatic coupling vectors. Applied to the photoisomerization of \textit{trans}-diimide, the scheme converges systematically as the scaling factor is increased and yields an excited-state lifetime in good agreement with previous nonadiabatic simulations based on static SCF.\@ These results establish real-time propagation as an efficient and numerically stable route to the adiabatic states and couplings required for first-principles surface hopping.

A partially linearized mapping approach to surface hopping (MASH-PLDM) for nonadiabatic dynamics and nonlinear spectroscopy
Jan Obermeier, Kasra Asnaashari, Jeremy O. Richardson
arXiv28 Sep 2026PreprintCC BY 4.0Full textPhysical chemistry Quantum physics & quantum informationarXiv
Ensuring Complete Consistency between Hops and Wavefunction Propagation in Fewest-Switches Surface Hopping
Jonathan R. Mannouch
arXiv13 Oct 2026PreprintCC BY 4.0Full textPhysical chemistryarXiv
A Perspective on Phase Space Electronic Structure Theory : From Its Surface Hopping Origins Through To Its Future Promise
Joseph E. Subotnik, Ethan Alguire, Nicole Bellonzi +20
arXiv20 Sep 2026PreprintarXiv licenceFull textPhysical chemistryarXiv
Resolving Photochemical Reaction Pathways Using Field-Induced Surface Hopping Simulation of fs-EUV-TRPES: The Case of Furan
Xincheng Miao, Toshinori Suzuki, Roland Mitrić
arXiv29 Oct 2026PreprintarXiv licenceFull textPhysical chemistry Atomic, molecular & optical physicsarXiv
Coordination Alone Does Not Passivate Surface Halide-Vacancy States in Lead Halide Perovskites
Christopher Gaspar Msigwa, Muhammad Mateen, Shibing Chu
ChemRxiv10 Sep 2026PreprintCC BY-NC-NDFull textGeneral chemistryChemRxiv

Cite

BibTeX RIS

BibTeX

@misc{zhou2026surface,
  title = {{Surface Hopping Dynamics on Adiabatic States Propagated with Real-Time TDDFT}},
  author = {Ruiyi Zhou and Jeremy O. Richardson},
  howpublished = {arXiv},
  year = {2026},
  month = oct,
  doi = {10.48550/arxiv.2610.41686},
  eprint = {2610.41686},
  archivePrefix = {arXiv},
  url = {https://arxiv.org/abs/2610.41686},
  note = {CC BY 4.0},
}

RIS

TY  - UNPB
TI  - Surface Hopping Dynamics on Adiabatic States Propagated with Real-Time TDDFT
AU  - Ruiyi Zhou
AU  - Jeremy O. Richardson
PY  - 2026
DA  - 2026/10/30
PB  - arXiv
DO  - 10.48550/arxiv.2610.41686
UR  - https://arxiv.org/abs/2610.41686
AB  - Real-time time-dependent density functional theory (RT-TDDFT) is widely used to simulate ultrafast electron dynamics, but it is usually coupled to the nuclei through the mean-field Ehrenfest approximation, which cannot describe wavepacket branching and violates detailed balance. Surface hopping avoids these problems, but has not previously been combined with RT-TDDFT because real-time propagation does not directly provide the necessary adiabatic states. In this work we introduce an energy-scaled time-dependent Kohn--Sham (TDKS) propagation scheme, motivated by the quantum adiabatic theorem. Scaling widens the separation between electronic and nuclear timescales, so that each propagated state follows the adiabatic surface selected by its initial condition: either the ground state or a non-Aufbau self-consistent-field (ΔSCF) solution. The propagation thereby avoids the convergence failures of static SCF solvers in regions of strong nonadiabatic coupling. Because the independently propagated states are complex-valued and not mutually orthogonal, we reformulate the mapping approach to surface hopping (MASH) in a complex adiabatic basis and introduce a dynamical transition orbital (DTO) gauge that restores a well-defined particle--hole representation for evaluating time-derivative couplings and nonadiabatic coupling vectors. Applied to the photoisomerization of \textit{trans}-diimide, the scheme converges systematically as the scaling factor is increased and yields an excited-state lifetime in good agreement with previous nonadiabatic simulations based on static SCF.\@ These results establish real-time propagation as an efficient and numerically stable route to the adiabatic states and couplings required for first-principles surface hopping.
ER  -

Abstract

Related

Cite