We present a computationally efficient molecular dynamics method, based on holonomic constraints, devised to estimate the rate constants of rare activated events of short duration. We assume that the process is described by a reaction coordinate ξ(r), a well-defined function in configuration space, and we constrain the system at the `bottleneck' region by prescribing the value of ξ(r). MD trajectories sample phase space according to a biased configurational distribution and averages can be taken from such a new Blue Moon ensemble, with suitable reweighting, to study rare events.
Rare events by constrained molecular dynamics / Ciccotti, Giovanni; M., Ferrario. - In: JOURNAL OF MOLECULAR LIQUIDS. - ISSN 0167-7322. - 89:1-3(2000), pp. 1-18. [10.1016/s0167-7322(00)90001-1]