Functional Analytic Derivation and CP2K Implementation of the SCCS Model Based on the Solvent-Aware Interface

TL;DR

This paper introduces a new solvent-aware SCCS model implementation in CP2K that effectively eliminates non-physical solvent regions and improves SCF convergence by using a convolution-based interface function.

Contribution

The authors develop a solvent-aware interface for SCCS in CP2K, addressing previous issues with non-physical solvent regions and providing a rigorous derivation of electrostatic contributions.

Findings

Successfully eliminates non-physical solvent regions within the solute.

Achieves improved SCF convergence in test cases.

Demonstrates effectiveness on bulk and surface models.

Abstract

In the self-consistent continuum solvation (SCCS) approach ($\textit{J. Chem. Phys.}$ 136, 064102 (2012)), the analytical expressions of the local solute-solvent interface functions determine the interface function and dielectric function values at a given real space position based solely on the electron density at that position, completely disregarding the surrounding electron density distribution. Therefore, the low electron density areas inside the solute will be identified by the algorithm as regions where implicit solvent exists, resulting in the emergence of non-physical implicit solvent regions within the solute and even potentially leading to the divergence catastrophe of Kohn-Sham SCF calculations. We present a new and efficient SCCS implementation based on the solvent-aware interface ($\textit{J. Chem. Theory Comput.}$ 15, 3, 1996-2009 (2019)) which addresses this issue by utilizing a solute-solvent interface function based on convolution of electron density in the CP2K software package, which is based on the mixed Gaussian and plane waves (GPW) approach. Starting with the foundational formulas of SCCS, we have rigorously and meticulously derived the contributions of the newly defined electrostatic energy to the Kohn-Sham potential and the analytical forces. This comprehensive derivation utilizes the updated versions of the solute-solvent interface function and the dielectric function, tailored to align with the specifics of the GPW implementation. Our implementation has been tested to successfully eliminate non-physical implicit solvent regions within the solute and achieve good SCF convergence, as demonstrated by test results for both bulk and surface models, namely liquid $H_2O$, titanium dioxide, and platinum.