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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

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Diabat Interpolation for Polymorph Free-Energy Differences.

Kartik Kamat¹, Baron Peters¹

¹Department of Chemical Engineering and ‡Department of Chemistry and Biochemistry, University of California , Santa Barbara, California 93106, United States.

The Journal of Physical Chemistry Letters

|January 18, 2017

Summary

This summary is machine-generated.

This study introduces a faster method for calculating free-energy differences between crystal polymorphs. It combines Bennett

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Area of Science:

Computational materials science
Statistical mechanics
Solid-state physics

Background:

Calculating free-energy differences between polymorphs is crucial for materials science.
Current methods often involve computationally expensive techniques like harmonic approximations or multistage free-energy perturbations.
Efficient and accurate methods are needed to overcome these limitations.

Purpose of the Study:

To develop a swift and efficient method for estimating free-energy differences between polymorphs.
To combine established techniques in a novel way to simplify free-energy calculations.
To reduce the computational cost associated with polymorph free-energy difference computations.

Main Methods:

The study combines Bennett's diabat interpolation method with energy gaps from lattice-switch Monte Carlo techniques.
This novel approach requires only two unbiased molecular dynamics simulations, one for each polymorph.
The method is validated by computing the free-energy difference between face-centered cubic (FCC) and body-centered cubic (BCC) polymorphs of a Gaussian core solid.

Main Results:

The proposed method provides a swift estimation of free-energy differences between polymorphs.
It significantly reduces the computational burden compared to existing approaches.
The free-energy difference between FCC and BCC polymorphs for a Gaussian core solid was successfully computed.

Conclusions:

The combination of Bennett's method and lattice-switch Monte Carlo offers an efficient route to calculate polymorph free-energy differences.
The method's reliance on only two unbiased simulations makes it highly practical.
The findings suggest potential parallels with methods used in electron transfer studies, particularly regarding parabolic models of free-energy diabats.