Variational tensor approach for approximating the rare-event kinetics of macromolecular systems

J Chem Phys. 2016 Feb 7;144(5):054105. doi: 10.1063/1.4940774.

Abstract

Essential information about the stationary and slow kinetic properties of macromolecules is contained in the eigenvalues and eigenfunctions of the dynamical operator of the molecular dynamics. A recent variational formulation allows to optimally approximate these eigenvalues and eigenfunctions when a basis set for the eigenfunctions is provided. In this study, we propose that a suitable choice of basis functions is given by products of one-coordinate basis functions, which describe changes along internal molecular coordinates, such as dihedral angles or distances. A sparse tensor product approach is employed in order to avoid a combinatorial explosion of products, i.e., of the basis set size. Our results suggest that the high-dimensional eigenfunctions can be well approximated with relatively small basis set sizes.

Publication types

  • Research Support, Non-U.S. Gov't