Improving the Efficiency of Variationally Enhanced Sampling with Wavelet-Based Bias Potentials

TL;DR

This paper introduces wavelet basis functions into variationally enhanced sampling (VES), demonstrating that wavelets improve convergence, robustness, and performance over traditional basis functions and metadynamics in sampling free energy landscapes.

Contribution

The study implements and validates Daubechies wavelets as basis functions for VES, showing their superior convergence and robustness compared to other basis functions.

Findings

Wavelets outperform traditional basis functions in convergence.

Wavelets provide more stable and consistent bias potentials.

Wavelets outperform metadynamics in sampling efficiency.

Abstract

Collective variable-based enhanced sampling methods are routinely used on systems with metastable states, where high free energy barriers impede proper sampling of the free energy landscapes when using conventional molecular dynamics simulations. One such method is variationally enhanced sampling (VES), which is based on a variational principle where a bias potential in the space of some chosen slow degrees of freedom, or collective variables, is constructed by minimizing a convex functional. In practice, the bias potential is taken as a linear expansion in some basis function set. So far, primarily basis functions delocalized in the collective variable space, like plane waves, Chebyshev, or Legendre polynomials, have been used. However, there has not been an extensive study of how the convergence behavior is affected by the choice of the basis functions. In particular, it remains an open question if localized basis functions might perform better. In this work, we implement, tune, and validate Daubechies wavelets as basis functions for VES\@. The wavelets construct orthogonal and localized bases that exhibit an attractive multiresolution property. We evaluate the performance of wavelet and other basis functions on various systems, going from model potentials to the calcium carbonate association process in water. We observe that wavelets exhibit excellent performance and much more robust convergence behavior than all other basis functions, as well as better performance than metadynamics. In particular, using wavelet bases yields far smaller fluctuations of the bias potential within individual runs and smaller differences between independent runs. Based on our overall results, we can recommend wavelets as basis functions for VES.