Related papers: Simulating electronic coherences induced by conica…
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…
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…
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…
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…
In response to a community prediction challenge, we simulate the nonadiabatic dynamics of cyclobutanone using the mapping approach to surface hopping (MASH). We consider the first 500 fs of relaxation following photo-excitation to the S2…
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…
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…
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…
An extension of the CCS-method [Chem. Phys. 2004, 304, p. 103-120] for simulating non-adiabatic dynamics with quantum effects of the nuclei is put forward. The time-dependent Schr\"{o}dinger equation for the motion of the nuclei is solved…
The recent improvement in experimental capabilities for interrogating and controlling molecular systems with ultrafast coherent light sources calls for the development of theoretical approaches that can accurately and efficiently treat…
Ab initio modeling of conical intersection dynamics is crucial for various photochemical, photophysical, and biological processes. However, adiabatic electronic states obtained from electronic structure computations involve random phases,…
Conical intersections (CoIn) dominate the pathways and outcomes of virtually all photophysical and photochemical molecular processes. Despite extensive experimental and theoretical effort, CoIns have not been directly observed yet and the…
Independent electron surface hopping (IESH) is a computational algorithm for simulating the mixed quantum-classical molecular dynamics of adsorbate atoms and molecules interacting with metal surfaces. It is capable of modelling the…
We report an implementation for employing the algebraic diagrammatic construction to second order [ADC(2)] ab initio electronic structure level of theory in nonadiabatic dynamics simulations in the framework of the SHARC (surface hopping…
We describe how to simulate charge diffusion in organic semiconductors using a recently introduced mixed quantum-classical method, the mapping approach to surface hopping (MASH). In contrast to standard fewest-switches surface hopping, this…
Nonadiabatic dynamics around an avoid crossing or a conical intersection play a crucial role in the photoinduced processes of most polyatomic molecules. The present work shows that the topological phase in conical intersection makes the…
The direct observation of non-adiabatic dynamics at conical intersections is a long-standing goal of molecular physics. Novel time-resolved spectroscopies have been proposed which are sensitive to electronic coherences induced by the…
Non-adiabatic dynamics simulations have become a standard approach to explore photochemical reactions. Such simulations require underlying potential energy surfaces and couplings between them, calculated at a chosen level of theory, yet…
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…
Rare nonadiabatic reactions are a key component of many important molecular processes but are challenging to capture with direct dynamical simulations. In this paper, we combine our recently developed mapping approach to surface hopping…