Many problems in materials science and biology involve particles interacting with strong, short-ranged bonds that can break and form on experimental timescales. Treating such bonds as constraints can significantly speed up sampling their equilibrium distribution, and there are several methods to sample probability distributions subject to fixed constraints. We introduce a Monte Carlo method to handle the case when constraints can break and form. More generally, the method samples a probability distribution on a stratification: a collection of manifolds of different dimensions, where the lower-dimensional manifolds lie on the boundaries of the higher-dimensional manifolds. We show several applications of the method in polymer physics, self-assembly of colloids, and volume calculation in high dimensions.
REFERENCES
The way κij is defined here gives it units of length. To obtain a dimensionless sticky parameter, we must write the argument of the delta function as δ(r/σij − 1). However, doing so would require carrying around factors of σij in our later calculations, so we instead work with a dimensional κij for notational convenience.
A dimensionless sticky parameter would be defined as .
Loosely, if two manifolds X, Y with dim(Y) < dim(X) are in the stratification, and , i.e., Y is in the closure of X, then at every point y ∈ Y, the stratification near y has to look locally like a cone, and furthermore, the topology of this local picture is the Same for all y ∈ Y. Specifically, a stratification is usually assumed to satisfy Whitney’s condition B at all y ∈ Y, which is as follows:28 Given X, Y as above, suppose that (i) sequence x1, x2, …, ∈ X converges to y, (ii) sequence y1, y2, …, ∈ Y converges to y, (iii) the secant lines converge to a limiting line l in some local coordinate system near y, and (iv) the tangent planes converge to a limiting plane τ. Then, l ⊂ τ.
We should really linearize q(x + hv + w), where w is an (unknown) vector in the normal space to MI at x. The contribution from w vanishes to linear order, since linearizing the equations qi(x + u) = 0, i ∈ Ieq defining manifold MI, gives . Therefore, any vector u that maintains the constraints to linear order must lie in the tangent space to MI at x.