Free energy disconnectivity graphs: Application to peptide models

Abstract

Disconnectivity graphs are widely used for understanding the multidimensional potential energy surfaces (PES) of complex systems. Since entropic contributions to the free energy can be important, particularly for polypeptide chains and other polymers, conclusions concerning the equilibrium properties and kinetics of the system based on potential energy disconnectivity graphs (PE DG) can be misleading. We present an approach for constructing free energy surfaces (FES) and free energy disconnectivity graphs (FE DG) and give examples of their applications to peptides. They show that the FES and FE DG can differ significantly from the PES and PE DG.