Towards the Irving Kirkwood limit of the mechanical stress tensor
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Published version
Author(s)
Smith, E
Heyes, D
Dini, D
Type
Journal Article
Abstract
The probability density functions (PDFs) of the local measure of pressure as a function of the sampling volume are computed for a model Lennard-Jones (LJ) fluid using the Method of Planes (MOP) and Volume Averaging (VA) techniques. This builds on the study of Heyes, Dini, and Smith [J. Chem. Phys. 145, 104504 (2016)] which only considered the VA method for larger subvolumes. The focus here is typically on much smaller subvolumes than considered previously, which tend to the Irving-Kirkwood limit where the pressure tensor is defined at a point. The PDFs from the MOP and VA routes are compared for cubic subvolumes, V=ℓ3. Using very high grid-resolution and box-counting analysis, we also show that any measurement of pressure in a molecular system will fail to exactly capture the molecular configuration. This suggests that it is impossible to obtain the pressure in the Irving-Kirkwood limit using the commonly employed grid based averaging techniques. More importantly, below ℓ≈3 in LJ reduced units, the PDFs depart from Gaussian statistics, and for ℓ=1.0, a double peaked PDF is observed in the MOP but not VA pressure distributions. This departure from a Gaussian shape means that the average pressure is not the most representative or common value to arise. In addition to contributing to our understanding of local pressure formulas, this work shows a clear lower limit on the validity of simply taking the average value when coarse graining pressure from molecular (and colloidal) systems.
Date Issued
2017-06-14
Date Acceptance
2017-05-20
Citation
Journal of Chemical Physics, 2017, 146
ISSN
1089-7690
Publisher
AIP Publishing
Journal / Book Title
Journal of Chemical Physics
Volume
146
Copyright Statement
© 2017 Author(s). All article content,
except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/).
except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/).
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/N025954/1
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
STATISTICAL-MECHANICS
INHOMOGENEOUS FLUIDS
PRESSURE TENSOR
DYNAMICS
SIMULATIONS
HYDRODYNAMICS
PARTICLE
SOLIDS
MODEL
Chemical Physics
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Publication Status
Published
Article Number
224109