Lennard-Jones Parameter Fitting for Gold/Water Interaction Based on Structural Analysis: A QM, MM, and QM/MM Study.

Area of Science:

• Computational chemistry
• Materials science
• Physical chemistry

Background:

• Accurate modeling of metal/water interfaces is essential across various scientific fields.
• Classical molecular dynamics (MD) often uses Lennard-Jones (LJ) potentials to describe these interactions.
• Existing LJ parameters may not precisely capture ab initio (DFT) metal/water interactions, necessitating improved parameterization.

Purpose of the Study:

• To develop improved Lennard-Jones (LJ) parameters for metal/water interactions.
• To enhance the description of water structuring on metal surfaces in classical MD simulations.
• To validate a novel parameter fitting approach based on structural analysis.

Main Methods:

• Classical MD simulations of gold/water interfaces with varied LJ parameters (sigma/epsilon).
• Comparison of simulated water structuring against density functional theory (DFT) results.
• Testing of developed LJ parameters in quantum mechanics/molecular mechanics (QM/MM) MD simulations.

Main Results:

• The proposed structural analysis approach yields improved LJ parameters compared to existing literature values.
• Simulations using the new parameters better reproduce DFT-observed water structuring on gold.
• Hybrid QM/MM calculations with the new parameters closely match QM-level water density profiles at reduced computational cost.

Conclusions:

• A novel, structure-based method effectively refines LJ parameters for metal/water interactions.
• The improved parameters enhance the accuracy of classical MD for modeling water on metallic surfaces.
• This approach offers a computationally efficient way to study complex metal/water systems.