3D Molecular Theory of Solvation for Nanochemistry in Solution

Statistical-mechanical, molecular theory of solvation (a.k.a. 3D-RISM-KH) predicts from the first principles the solvation structure and thermodynamics of nanosystems and properly accounts for chemical functionalities by representing both electrostatic and non-polar features of solvation structure such as hydrogen bonding and solvophobicity, salt bridges, structural solvent, associative and electrochemical effects. We coupled 3D-RISM-KH with ab initio methods in a self-consistent field description (including analytical gradients) of electronic structure, optimized geometry, and chemical reactions in solution, and have extensively validated the KS-DFT/3D-RISM-KH multiscale method against experimental data for solvation thermochemistry, conformational equilibria, tautomerization energies and activation barriers in different solvents. The method explains the electronic and solvation structure of ionic liquids; mechanisms of self-assembly, conformational stability and solvent-driven supramolecular chirality of synthetic organic rosette nanotubes; and mechanisms of supercapacitance in nanoporous carbon electrodes.