Stochastic quasi-Newton molecular simulations

Abstract

We report a new and efficient factorized algorithm for the determination of the adaptive compound mobility matrix B in a stochastic quasi-Newton method (S-QN) that does not require additional potential evaluations. For one-dimensional and two-dimensional test systems, we previously showed that S-QN gives rise to efficient configurational space sampling with good thermodynamic consistency [C. D. Chau, G. J. A. Sevink, and J. G. E. M. Fraaije, J. Chem. Phys. 128, 244110 (2008)]. Potential applications of S-QN are quite ambitious, and include structure optimization, analysis of correlations and automated extraction of cooperative modes. However, the potential can only be fully exploited if the computational and memory requirements of the original algorithm are significantly reduced. In this paper, we consider a factorized mobility matrix B=JJ(T) and focus on the nontrivial fundamentals of an efficient algorithm for updating the noise multiplier J . The new algorithm requires O(n2) multiplications per time step instead of the O(n3) multiplications in the original scheme due to Choleski decomposition. In a recursive form, the update scheme circumvents matrix storage and enables limited-memory implementation, in the spirit of the well-known limited-memory Broyden-Fletcher-Goldfarb-Shanno (L-BFGS) method, allowing for a further reduction of the computational effort to O(n). We analyze in detail the performance of the factorized (FSU) and limited-memory (L-FSU) algorithms in terms of convergence and (multiscale) sampling, for an elementary but relevant system that involves multiple time and length scales. Finally, we use this analysis to formulate conditions for the simulation of the complex high-dimensional potential energy landscapes of interest.