Solvation Lies Within: Simulating Condensed-Phase Properties from Local Electronic Structures

Area of Science:

• Physical Chemistry
• Computational Chemistry
• Quantum Chemistry

Background:

• Simulating molecular responses to environmental changes, like energy shifts, is crucial but challenging.
• Accurate modeling of solvation effects is vital for understanding molecular behavior in condensed phases.

Purpose of the Study:

• To develop a robust protocol for efficiently sampling solvation effects in homogeneous condensed phases.
• To focus on local electronic structure perturbations for accurate energy shift simulations.

Main Methods:

• Utilizing an exact decomposition of total energies from Kohn-Sham density functional theory (KS-DFT).
• Employing a basis of spatially localized molecular orbitals.
• Focusing on perturbations to local electronic structures to model solvation.

Main Results:

• Chemically intuitive binding energies for water, ethanol, and acetonitrile were obtained.
• Fast convergence with respect to bulk size was observed.
• Results showed invariance to basis set choice but sensitivity to density functional approximations.

Conclusions:

• The developed protocol provides a physically sound and efficient method for estimating bulk solvation effects.
• The approach allows for accurate simulation of molecular energy shifts in condensed phases.
• This method offers a valuable tool for physical chemistry research.