Topical Review - Computational Methods
A maximum caliber approach for continuum path ensembles
van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, PO Box 94157, 1090 GD, Amsterdam, The Netherlands
2 Department of Chemistry, University of Cambridge, CB2 1EW, Cambridge, UK
Accepted: 5 July 2021
Published online: 23 September 2021
The maximum caliber approach implements the maximum entropy principle for trajectories by maximizing a path entropy under external constraints. The maximum caliber approach can be applied to a diverse set of equilibrium and non-equilibrium problems concerning the properties of trajectories connecting different states of a system. In this review, we recapitulate the basic concepts of the maximum entropy principle and of its maximum caliber implementation for path ensembles, and review recent applications of this approach. In particular, we describe how we recently used this approach to introduce a framework, called here the continuum path ensemble maximum caliber (CoPE-MaxCal) method, to impose kinetic constraints in molecular simulations, for instance to include experimental information about transition rates. Such incorporation of dynamical information can ameliorate inaccuracies of empirical force fields, and lead to improved mechanistic insights. We conclude by offering an outlook for future research.
© The Author(s) 2021
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