The estimate of free energy profiles of chemical reactions is of great interest andyet presents major challenges related to the exploration of phase space. Pathcollective variables (PCVs) allow describing complex chemical processes with asimple bi-dimensional representation of the free energy landscape (1). Here, wecouple PCVs with enhanced sampling techniques (e.g. umbrella sampling,metadynamics, etc.), demonstrating that this approach is able to catch most ofthe complexity inherent to chemical reactions. We will also show theacceleration of the convergence obtained through a refinement procedure. As atest case we present the methyl phosphate hydrolysis studied via DFT moleculardynamics. The investigation of this reaction, well studied in the past, willshow the non-trivial nature of cooperative motions along the reaction pathway,which are now explicitly taken into account.  1. Branduardi, D.; Gervasio, F.L.; Parrinello, M; J. Chem. Phys. 2007.

Free energy calculations
with path collective variables: The case of methyl phosphate hydrolysis

239th National Meeting (2010)

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Free energy calculations with path collective variables: The case of methyl phosphate hydrolysis