Entropy associated with conformation and density fluctuations in biomolecular solutions

Abstract

Microscopic formula to describe the entropy of biomolecular solutions are derived based on the Gibbs formula of entropy, and the generalized Langevin theory combined with the RISM/3D-RISM theory. Two formula are derived: one is concerned with the conformational fluctuation of a biomolecule, and the other with the density fluctuation of solvent around a solute. The formula derived for the entropy associated with the conformational fluctuation is where N is the number of atoms in the solute, and A is the determinant of the inverse of the variance-covariance matrix of conformational fluctuation. The formula for the entropy of solvent at a pair of positions around a solute is also derived to be, where n is the number of atoms in a solvent molecule, and B is essentially the determinant of the matrix of the density-pair-correlation functions. The entropy at a local position r may be obtained by integrating the expression by over the entire volume of the system. The feasibility of the calculation to find the entropies is discussed.