Related papers: On the inclusion of the diagonal Born-Oppenheimer …
Ring polymer surface hopping (RPSH) is a mixed quantum-classical dynamics method for incorporating nuclear quantum effects (NQEs) into nonadiabatic dynamics simulations via the extended phase-space of a classical ring polymer. Here, we…
This report presents a new approach for treating the coupling of electrons and nuclei in quantum mechanical calculations for molecules and condensed matter. It includes the standard "Born-Oppenheimer approximation" as a special case but…
The diagonal nonadiabatic term arising from the Born--Oppenheimer wave-function ansatz contains contributions from a vector and scalar potential. The former is provably zero when the wave function can be taken to be real valued, and the…
Surface hopping algorithms, as an important class of quantum dynamics simulation algorithms for non-adiabatic dynamics, are typically performed in the adiabatic representation, which can break down in the presence of ill-defined adiabatic…
This work identifies geometric effects on dynamics due to nonadiabatic couplings in Born Oppenheimer systems and provides a systematic method for deriving corrections to mixed quantum-classical methods. Specifically, an exact path integral…
Nuclear Berry curvature effects emerge from electronic spin degeneracy and canlead to non-trivial spin-dependent (nonadiabatic) nuclear dynamics. However, such effects are completely neglected in all current mixed quantum-classical methods…
We perform extensive benchmark comparisons of surface hopping dynamics with numerically exact calculations for the spin-boson model over a wide range of energetic and coupling parameters as well as temperature. We find that deviations from…
It is well known that fewest-switches surface hopping (FSSH) fails to correctly capture the quadratic scaling of rate constants with diabatic coupling in the weak-coupling limit, as expected from Fermi's golden rule and Marcus theory. To…
The adiabatic Born-Oppenheimer approximation is considered to be a robust approach that very rarely breaks down. Consequently, it is predominantly utilized to address various electron-phonon properties in condensed matter physics. By…
While the treatment of conical intersections in molecular dynamics generally requires nonadiabatic approaches, the Born-Oppenheimer adiabatic approximation is still adopted as a valid alternative in certain circumstances. In the context of…
The quantum reprojection method within the standard adiabatic Born-Oppenheimer approach is derived for multielectron collision systems. The method takes nonvanishing asymptotic nonadiabatic couplings into account and distinguishes…
We present a nonadiabatic classical-trajectory approach that offers the best of both worlds between fewest-switches surface hopping (FSSH) and quasiclassical mapping dynamics. This mapping approach to surface hopping (MASH) propagates the…
We consider non-adiabatic transitions in multiple dimensions, which occur when the Born-Oppenheimer approximation breaks down. We present a general, multi-dimensional algorithm which can be used to accurately and efficiently compute the…
We investigate two well-known approaches for extending the fewest switches surface hopping (FSSH) algorithm to periodic time-dependent couplings. The first formalism acts as if the instantaneous adiabatic electronic states were standard…
We revisit a recent proposal to model nonadiabatic problems with a complex-valued Hamiltonian through a phase-space surface hopping (PSSH) algorithm employing a pseudo-diabatic basis. Here, we show that such a pseudo-diabatic PSSH (PD-PSSH)…
We carried out extensive studies to examine the performance of the fewest-switches surface hopping method in the description of the ultrafast intersystem crossing dynamic of various singlet-triplet (S-T) models by comparison with the…
Non-adiabatic chemical reactions involving continuous circularly polarized light (cw CPL) have not attracted as much attention as dynamics in unpolarized/linearly polarized light. However, including circularly (in contrast to linearly)…
Ring Polymer Surface-Hopping (RPSH) has been recently introduced as a well-tailored method for incorporating nuclear quantum effects (NQEs), such as zero-point energy and tunneling, into non-adiabatic molecular dynamics simulations. The…
The choice of the electronic representation in on-the-fly quantum dynamics is crucial. The adiabatic representation is appealing since adiabatic states are readily available from quantum chemistry packages. The nuclear wavepackets are then…
This research examines the nonadiabatic dynamics of cyclobutanone after excitation into the n-3s Rydberg S2 state. It stems from our contribution to the Special Topic of the Journal of Chemical Physics to test the predictive capability of…