Per|Mut: Spatially Resolved Hydration Entropies from Atomistic Simulations

Area of Science:

• Biophysics
• Computational Chemistry
• Thermodynamics

Background:

• The hydrophobic effect is crucial for biophysical processes, driven by hydration shell enthalpy and entropy.
• Calculating solvation entropies is computationally challenging due to vast configuration spaces.
• Local hydration entropy descriptions are needed to understand effects of molecular features.

Purpose of the Study:

• Introduce and evaluate the novel Per|Mut method for calculating spatially resolved hydration entropies.
• Address the sampling problem in solvation entropy calculations.
• Enable local analysis of hydration entropy contributions.

Main Methods:

• Developed the Per|Mut method utilizing permutation reduction (N! alleviation).
• Employed a third-order mutual information expansion for entropy calculation.
• Applied the method to argon, n-alkanes, and octanol systems.

Main Results:

• Per|Mut effectively alleviates sampling challenges in entropy calculations.
• The method provides spatially resolved hydration entropy data.
• Successful application demonstrated on model systems.

Conclusions:

• Per|Mut offers a viable approach for detailed hydration entropy analysis.
• The method facilitates understanding local contributions to the hydrophobic effect.
• Spatially resolved entropy calculations are now more accessible.