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Density correlation in liquid surfaces: Bedeaux-Weeks high order terms and non capillary wave background
Jose Hernández-Muñoz1, Enrique Chacón2, Pedro Tarazona3
1Departamento de Física Teórica de la Materia Condensada, IFIMAC Condensed Matter Physics Center, Universidad Autónoma de Madrid, Madrid 28049, Spain.
The Journal of Chemical Physics
|October 4, 2018
Summary
Molecular Dynamics simulations quantitatively test capillary wave theory for liquid-vapor surfaces. Bedeaux-Weeks theory accurately captures density correlations, differing significantly from Wertheim
Area of Science:
- Physical Chemistry
- Computational Physics
Background:
- Capillary wave (CW) theory describes fluctuations at liquid-vapor interfaces.
- Bedeaux and Weeks (BW) developed a theory in 1985 for CW effects on density correlations.
- Wertheim's proposal is the first term in the BW series.
Purpose of the Study:
- To quantitatively test the 1985 Bedeaux-Weeks theory for capillary wave effects on density correlations.
- To compare simulation results with Wertheim's proposal and BW theory.
- To propose a method for analyzing non-CW fluctuations.
Main Methods:
- Molecular Dynamics (MD) simulations of liquid-vapor surfaces.
- Intrinsic Sampling Method analysis.
- Comparison with theoretical predictions (BW and Wertheim).
Main Results:
- MD simulations provide a quantitative test for BW theory.
- BW theory accurately predicts density correlations, differing from Wertheim's proposal.
- A computational method for non-CW fluctuations was developed.
Conclusions:
- Bedeaux-Weeks theory is accurate and necessary for understanding density correlations.
- The theory's predictions differ significantly from Wertheim's simpler proposal.
- Findings have implications for analyzing X-ray surface diffraction and MD simulation data.
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