The harmonic superposition method provides a unified framework to the equilibrium and relaxation kinetics on complex potential energy landscapes. Here we extend it to grand-canonical statistical ensembles governed by chemical potentials or chemical potential differences, by sampling energy minima corresponding to the various relevant sizes or compositions. The method is applied and validated against conventional Monte Carlo simulations for the problems of chemical equilibrium in nanoalloys and hydrogen absorption in bulk and nanoscale palladium. (C) 2015 Elsevier B.V. All rights reserved.