Dynamical Rare event simulation techniques for equilibrium and non-equilibrium systems

Abstract

I give an overview of rare event simulation techniques to generate dynamical pathways across high free energy barriers. The methods on which I will concentrate are the reactive flux approach, transition path sampling, (replica-exchange) transition interface sampling, partial path sampling/milestoning, and forward flux sampling. These methods have in common that they aim to simulate true molecular dynamics trajectories at a much faster rate than naive brute force molecular dynamics. The advantages and disadvantages of these methods are discussed and compared for a simple one-dimensional test system. These numerical results reveal some important pitfalls of the present non-equilibrium methods that have no easy solution and show that caution is necessary when interpreting their results.