Simplified continuum solvent model with a smooth cavity based on volumetric data.

Area of Science:

• Computational chemistry
• Theoretical chemistry
• Physical chemistry

Background:

• Continuum solvent models (CSMs) are crucial for simulating chemical systems in solution.
• Existing CSMs often employ complex cavity definitions.
• Accurate solvation energy prediction is vital for understanding chemical reactions.

Purpose of the Study:

• To introduce a novel continuum solvent model (CSM) with a smooth, easily defined cavity for grid-based electronic structure calculations.
• To validate the model's ability to reproduce experimental partial molar volumes.
• To assess the accuracy of the CSM for predicting solvation energies in various solvent environments.

Main Methods:

• Developed a smooth cavity definition based on atomic van der Waals radii and a single size-controlling parameter.
• Utilized a binary mixture's distribution function to define the solvent-accessible surface.
• Applied the CSM to predict aqueous solvation Gibbs energies, non-aqueous energetics (spiropyran/merocyanin), proton transfer, and electrostatic screening of gold clusters.

Main Results:

• The model accurately reproduces experimental partial molar volumes with a single parameter.
• The CSM demonstrates accuracy comparable to other smooth-cavity models for aqueous solvation energies.
• Successful application to diverse non-aqueous systems, including complex reaction energetics and charged cluster solvation.

Conclusions:

• The proposed smooth cavity definition offers a robust and accurate approach for continuum solvent modeling.
• The developed CSM provides a reliable tool for electronic structure calculations in both aqueous and non-aqueous media.
• This model advances the simulation of solvation effects in complex chemical and physical systems.