Related papers: Surface hopping from the perspective of quantum-cl…
Mixed quantum-classical methods provide powerful algorithms for the simulation of quantum processes in large and complex systems. The forward-backward trajectory solution of the mixed quantum-classical Liouville equation in the mapping…
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…
Two-frequency (two-color) laser fields provide a powerful and flexible means for steering molecular dynamics. However, quantitatively reliable and scalable theoretical tools for simulating laser-driven nonadiabatic processes under such…
The fewest switches surface hopping (FSSH) method proposed by Tully in 1990 [J. C Tully, J. Chem. Phys. 93, 1061 (1990)] -- along with its many later variations -- is basis for most practical simulations of molecular dynamics with…
Dynamical transitions, such as a change from bound to unbound motion, often occur as post-adiabatic crossings of a time-dependent separatrix. Whether or not any given orbit will include such a crossing transition typically depends…
We present a method to study rare nonadiabatic dynamics in open quantum systems using transition path sampling and quantum jump trajectories. As with applications of transition path sampling to classical dynamics, the method does not rely…
A semicalssical method based on surface-hopping techniques is developed to model the dynamics of radiative association with electronic transitions in arbitrary polyatomic systems. It can be proven that our method is an extension of the…
Incorporating nuclear quantum effects into nonadiabatic dynamics remains a significant challenge. Herein we introduce new nonadiabatic dynamics approaches based on the recently developed constrained nuclear-electronic orbital (CNEO) theory.…
In this work, surface diffusion is studied with a different perspective by showing how the corresponding open dynamics is transformed when passing, in a continuous and smooth way, from a pure quantum regime to a full classical regime; the…
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…
Mixed-quantum classical (MQC) methods for simulating the dynamics of molecules at metal surfaces have the potential to accurately and efficiently provide mechanistic insight into reactive processes. Here, we introduce simple two-dimensional…
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…
We show how the dynamically nonlocal formulation of classical nuclear motion in the presence of quantal electronic transitions presented many years ago by Pechukas can be localized in time using time dependent perturbation theory to give an…
A surface-hopping algorithm recently derived from the exact factorization approach, SHXF, [Ha, Lee, Min, J. Phys. Chem. Lett. 9, 1097 (2018)] introduces an additional term in the electronic equation of surface-hopping, which couples…
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 consider the quantum and classical Liouville dynamics of a non-integrable model of two coupled spins. Initially localised quantum states spread exponentially to the system dimension when the classical dynamics are chaotic. The long-time…
Trajectory-based mixed quantum-classical approaches to coupled electron-nuclear dynamics suffer from well-studied problems such as the lack of (or incorrect account for) decoherence in the trajectory surface hopping method and the inability…
We present an efficient \textit{ab initio} algorithm for quantum dynamics simulations of interacting systems that is based on the conditional decomposition of the many-body wavefunction [Phys. Rev. Lett. 113, 083003 (2014)]. Starting with…
We present a semiclassical quantization condition, i.e., quantum-classical correspondence, for steady states of nonadiabatic systems consisting of fast and slow degrees of freedom (DOFs) by extending Gutzwiller's trace formula to a…
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…