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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…
Fewest switches surface hopping (FSSH) is a well benchmarked dynamical method for simulating nonadiabatic systems. In particular, the literature shows that for the spin-Boson model Hamiltonian, FSSH with appropriate corrections usually…
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…
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…
This work presents a strategy to efficiently and safely account for decoherence in the fewest switches surface hopping method. Standard decoherence corrections often lead to too strong coherence suppression. A simple and general solution to…
A new scheme is proposed for modeling molecular nonadiabatic dynamics near metal surfaces. The charge-transfer character of such dynamics is exploited to construct an efficient reduced representation for the electronic structure. In this…
Fewest-switches surface hopping (FSSH) is the most popular method for simulating photochemical processes of molecular systems. Recently, we have constructed long short-term memory (LSTM) networks as a propagator for electronic subsystems in…
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…
Trajectory surface hopping (TSH) is one of the most widely used quantum-classical algorithms for nonadiabatic molecular dynamics. Despite its empirical effectiveness and popularity, a rigorous derivation of TSH as the classical limit of a…
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…
In this work, we employ trajectory-based simulations to predict the electronic coherences created by nonadiabatic dynamics near conical intersections. The mapping approach to surface hopping (MASH) is compared with standard fewest-switches…
While surface-hopping has emerged as a powerful method to simulate non-adiabatic dynamics in large molecules, the ad hoc nature of the necessary velocity adjustments and decoherence corrections in the algorithm somewhat reduces its…
Recently, the mapping approach to surface hopping (MASH) was proposed as a method to simulate the non-adiabatic dynamics of two-level systems. It was shown that the method possesses many desirable qualities, both theoretically and through…
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…
In open quantum systems decoherence occurs through interaction of a quantum subsystem with its environment. The computation of expectation values requires a knowledge of the quantum dynamics of operators and sampling from initial states of…
The diagonal Born-Oppenheimer correction (DBOC) stems from the diagonal second derivative coupling term in the adiabatic representation, and it can have an arbitrary large magnitude when a gap between neighbouring Born-Oppenheimer (BO)…
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…
Efficient descriptions of open quantum systems can be obtained by performing an adiabatic elimination of the fast degrees of freedom and formulating effective operators for the slow degrees of freedom in reduced dimensions. Here, we perform…
The violation of detailed balance poses a serious problem for the majority of current quasiclassical methods for simulating nonadiabatic dynamics. In order to analyze the severity of the problem, we predict the long-time limits of the…
We develop a multi-state generalisation of the recently proposed mapping approach to surface hopping (MASH) for the simulation of electronically nonadiabatic dynamics. This new approach extends the original MASH method to be able to treat…