How to compute density fluctuations at the nanoscale

TL;DR

This paper introduces a modified pair distribution function to accurately compute nanoscale density fluctuations, correcting finite-size effects and enabling local compressibility measurements at the nanometer scale.

Contribution

It presents a new method that accounts for particle size in fluctuation calculations, improving accuracy at the nanoscale.

Findings

Compressibility is size-independent for 1D hard sphere fluid.

The new method eliminates leading finite-size effects.

Enables accurate density fluctuation computation in small volumes.

Abstract

The standard definition of particle number fluctuations based on point-like particles neglects the excluded volume effect. This leads to a large and systematic finite-size scaling and an unphysical surface term in the isothermal compressibility. We correct these errors by introducing a modified pair distribution function which takes account of the finite size of the particles. For the hard sphere fluid in one-dimension, we show that the compressibility is strictly size-independent and we reproduce this result from the number fluctuations calculated with the new theory. In general, the present method eliminates the leading finite-size effect, which makes it possible to compute density fluctuations accurately in very small sampling volumes, comparable to the single particle size. These findings open the way for obtaining the local compressibility from fluctuation theory at the nanometer scale.