J. Stefanovic et Cc. Pantelides, Molecular dynamics as a mathematical mapping. II. Partial derivatives in the microcanonical ensemble, MOL SIMULAT, 26(3), 2001, pp. 167-192
Performing molecular dynamics in a fully continuous and differentiable fram
ework can be viewed as a deterministic mathematical mapping between, on one
side, the force field parameters that describe the potential energy intera
ctions and input macroscopic conditions, and, on the other, the calculated
corresponding macroscopic properties of the bulk molecular system.
Within this framework, it is possible to apply standard methods of variatio
nal calculus for the computation of the partial derivatives of the molecula
r dynamics mapping based on the integration of either the adjoint equations
or the sensitivity equations of the classical Newtonian equations of motio
n. We present procedures for these computations in the standard microcanoni
cal (N, V, E) ensemble, and compare the computational efficiency of the two
approaches. The general formulations developed are applied to the specific
example of bulk ethane fluid.
With these procedures in place, it is now possible to compute the partial d
erivatives of any property determined by molecular dynamics with respect to
any input property and any potential parameter. Moreover, these derivative
s are computed to essentially the same level of numerical accuracy as the o
utput properties themselves.