Related papers: On transition rates in surface hopping
In the paper we derive a semiclassical model for surface hopping allowing quantum dynamical non-adiabatic transition between different potential energy surfaces in which cases the classical Born-Oppenheimer approximation breaks down. The…
We study a two-level transition probability for a finite number of avoided crossings with a small interaction. Landau-Zener formula, which gives the transition probability for one avoided crossing as $e^{-\pi\frac{\varepsilon^{2}}{h}}$,…
The Landau--Zener (LZ) type classical-trajectory surface-hopping algorithm is applied to the nonadiabatic nuclear dynamics of the ammonia cation after photoionization of the ground-state neutral molecule to the excited states of the cation.…
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 implement a rare-event sampling scheme for quantifying the rate of thermally-activated nonadiabatic transitions in the condensed phase. Our QM/MM methodology uses the recently developed INAQS package to interface between an elementary…
We demonstrate that, for systems with spin-orbit coupling and an odd number of electrons, the standard fewest switches surface hopping (FSSH) algorithm does not conserve the total linear or angular momentum. This lack of conservation arises…
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…
Fewest-switches surface hopping (FSSH) has emerged as one of the leading methods for modeling the quantum dynamics of molecular systems. While its original formulation was limited to adiabatic populations, the growing interest in the…
We develop a surface hopping algorithm based on frozen Gaussian approximation for semiclassical matrix Schr\"odinger equations, in the spirit of Tully's fewest switches surface hopping method. The algorithm is asymptotically derived from…
The Landau-Zener formula provides the probability of non-adiabatic transitions occuring when two energy levels are swept through an avoided crossing. The formula is derived here in a simple calculation that emphasizes the physics…
In the spirit of the fewest switches surface hopping, the frozen Gaussian approximation with surface hopping (FGA-SH) method samples a path integral representation of the non-adiabatic dynamics in the semiclassical regime. An improved…
Nonadiabatic dynamics methods are an essential tool for investigating photochemical processes. In the context of employing first principles electronic structure techniques, such simulations can be carried out in a practical manner using…
We present a rare event sampling scheme applicable to coupled electronic excited states. In particular, we extend the forward flux sampling (FFS) method for rare event sampling to a nonadiabatic version (NAFFS) that uses the trajectory…
Non-adiabatic molecular dynamics (NAMD) has become an essential computational technique for studying the photophysical relaxation of molecular systems after light absorption. These phenomena require approximations that go beyond the…
This study introduces the FSSH-2 scheme, a redefined and numerically stable adiabatic Fewest Switches Surface Hopping (FSSH) method for mixed quantum-classical dynamics. It reformulates the standard FSSH hopping probability without…
The powerful molecular dynamics (MD) simulation is basically based on a picture that the atoms experience classical-like trajectories under the exertion of classical force field determined by the quantum mechanically solved electronic…
The capability of fewest-switches surface hopping (FSSH) to describe non-adiabatic dynamics of small and medium sized molecules under explicit excitation with external fields is evaluated. Different parameters in FSSH and combinations…
We develop a density matrix formalism to describe coupled electron-nuclear dynamics. To this end we introduce an effective Hamiltonian formalism that describes electronic transitions and small (quantum) nuclear fluctuations along a…
We investigate the transition of a quantum wave-packet through a one-dimensional avoided crossing of molecular energy levels when the energy levels at the crossing point are tilted. Using superadiabatic representations, and an approximation…
In this work, we describe various improved implementations of the mapping approach to surface hopping (MASH) for simulating nonadiabatic dynamics. These include time-reversible and piecewise-continuous integrators, which is only formally…