Dominant folding pathways of a peptide chain from ab initio quantum-mechanical simulations

Using the dominant reaction pathways method, we perform an ab initio quantum-mechanical simulation of a conformational transition of a peptide chain. The method we propose makes it possible to investigate the out-of-equilibrium dynamics of these systems, without resorting to an empirical representation of the molecular force field. It also allows to study rare transitions involving rearrangements in the electronic structure. By comparing the results of the ab initio simulation with those obtained by employing a standard force field, we discuss its capability to describe the nonequilibrium dynamics of conformational transitions. (C) 2011 American Institute of Physics. [doi:10.1063/1.3514149]