Efficient molecular density functional theory using generalized spherical harmonics expansions

doi:10.1063/1.4994281

Efficient molecular density functional theory using generalized spherical harmonics expansions

2017-09-07

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DOI：10.1063/1.4994281

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We show that generalized spherical harmonics are well suited for representing the space and orientation molecular density in the resolution of the molecular density functional theory. We consider the common system made of a rigid solute of arbitrary complexity immersed in a molecular solvent, both represented by molecules with interacting atomic sites and classical force fields. The molecular solvent density rho(r, Omega) around the solute is a function of the position r equivalent to (x, y, z) and of the three Euler angles Omega equivalent to (theta, phi, psi) describing the solvent orientation. The standard density functional, equivalent to the hypernetted-chain closure for the solute-solvent correlations in the liquid theory, is minimized with respect to rho(r, Omega). The up-to-now very expensive angular convolution products are advantageously replaced by simple products between projections onto generalized spherical harmonics. The dramatic gain in speed of resolution enables to explore in a systematic way molecular solutes of up to nanometric sizes in arbitrary solvents and to calculate their solvation free energy and associated microscopic solvent structure in at most a few minutes. We finally illustrate the formalism by tackling the solvation of molecules of various complexities in water. Published by AIP Publishing.

Keywords:

SOLVATION FREE-ENERGIES

INTEGRAL-EQUATION THEORY

HYDRATION FREE-ENERGIES

INTERACTION SITE MODEL

ORNSTEIN-ZERNIKE

INVARIANT EXPANSION

WATER

LIQUID

COMPUTATION

FLUIDS

Efficient molecular density functional theory using generalized spherical harmonics expansions

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