Extracting bulk properties of self-assembling systems from small simulations

摘要

For systems that self assemble into finite-sized objects, it is sometimesconvenient to compute the thermodynamics for a small system where a singleassembly can form. However, we show that in the canonical ensemble the use ofsmall systems can lead to significant finite-size effects due to thesuppression of concentration fluctuations. We introduce methods to estimate thebulk-yields from simulations of small systems and to follow the convergence ofyields with system size, under the assumptions that the various species behaveideally. We also propose an extension to the umbrella sampling technique thatallows the formation of multiple finite-sized objects.