Nonadiabatic Field: A Conceptually Novel Approach for Nonadiabatic Quantum Molecular Dynamics DOI Creative Commons
Baihua Wu, Bingqi Li, Xin He

et al.

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Reliable trajectory-based nonadiabatic quantum dynamics methods at the atomic/molecular level are critical for practical understanding and rational design of many important processes in real large/complex systems, where dynamical behavior electrons that nuclei coupled. The paper reports latest progress field (NaF), a conceptually novel approach with independent trajectories. Substantially different from mainstreams Ehrenfest-like surface hopping methods, nuclear force NaF involves arising coupling between electronic states, addition to adiabatic contributed by single state. is capable faithfully describing interplay motion broad regime, which covers relevant states keep coupled wide range or all time bifurcation characteristic essential. derived exact generalized phase space formulation coordinate-momentum variables, constraint (CPS) employed discrete electronic-state degrees freedom (DOFs) infinite Wigner used continuous DOFs. We propose efficient integrators equations both diabatic representations. Since formalism CPS not unique, can principle be implemented various representations correlation function (TCF) time-dependent property. They applied suite representative gas-phase condensed-phase benchmark models numerically results available comparison. It shown relatively insensitive representation TCF will potential tool reliable simulations mechanical transition systems.

Language: Английский

Conical Intersections Studied by the Configuration-Interaction-Corrected Tamm–Dancoff Method DOI
Lei Xu, Victor M. Freixas, Flavia Aleotti

et al.

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Conical intersections directly mediate the internal energy conversion in photoinduced processes a wide range of chemical and biological systems. Because Brillouin theorem, many conventional electronic structure methods, including configuration interaction with single excitations from Hartree-Fock reference time-dependent density functional theory either linear response approximation (TDDFT) or Tamm-Dancoff (DFT-TDA), have wrong dimensionality for conical between ground state (S0) first excited (S1) same multiplicity. This leads to unphysical crossings. Here, we implement assess configuration-interaction-corrected (CIC-TDA) that restores correct by coupling intersecting state. We apply CIC-TDA method S1/S0 ammonia (NH3), ethylene (C2H4), bithiophene (C8H6S2), azobenzene (C12H10N2), 11-cis retinal protonated Schiff base (PSB11) vacuo. show this black-box approach can produce potential surfaces (PESs) comparable accuracy multireference wave function methods. The validated here allow cost-efficient explorations electronically nonadiabatic dynamics, especially large molecules complex

Language: Английский

Citations

0
Nonadiabatic Field: A Conceptually Novel Approach for Nonadiabatic Quantum Molecular Dynamics DOI Creative Commons
Baihua Wu, Bingqi Li, Xin He

et al.

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Reliable trajectory-based nonadiabatic quantum dynamics methods at the atomic/molecular level are critical for practical understanding and rational design of many important processes in real large/complex systems, where dynamical behavior electrons that nuclei coupled. The paper reports latest progress field (NaF), a conceptually novel approach with independent trajectories. Substantially different from mainstreams Ehrenfest-like surface hopping methods, nuclear force NaF involves arising coupling between electronic states, addition to adiabatic contributed by single state. is capable faithfully describing interplay motion broad regime, which covers relevant states keep coupled wide range or all time bifurcation characteristic essential. derived exact generalized phase space formulation coordinate-momentum variables, constraint (CPS) employed discrete electronic-state degrees freedom (DOFs) infinite Wigner used continuous DOFs. We propose efficient integrators equations both diabatic representations. Since formalism CPS not unique, can principle be implemented various representations correlation function (TCF) time-dependent property. They applied suite representative gas-phase condensed-phase benchmark models numerically results available comparison. It shown relatively insensitive representation TCF will potential tool reliable simulations mechanical transition systems.

Language: Английский

Citations

0