Estimating Irving-Kirkwood pressure profiles from per-atom virial and density profiles: a closure for the contour-dependent term in planar liquid films
Abstract
The local pressure tensor of an inhomogeneous fluid is not unique. Two tangential profiles are in common use in planar simulations: the Irving-Kirkwood (IK) profile, which requires a dedicated pass over every pair of atoms for every slab, and the per-atom virial (PAV) profile, which molecular-dynamics codes produce at negligible cost and coincides with the Harasima contour. The two differ by the derivative of a pair quantity, P_T^IK - P_T^PAV = dQ/dz. We show that, for Lennard-Jones free-standing films, Q(z) can be predicted from the density profile and the bulk radial distribution function of the coexisting liquid: under the closure rho2(r1,r2) ~ rho(z1) rho(z2) g(r12), with a pair-local interpolation of g between its liquid and dilute limits, Q is a double integral of rho(z) against a kernel built from u'(r) g(r). The estimator P_T^IK,est = P_T^PAV + dQ/dz is tested against IK profiles measured on the same trajectories for 20 films (thicknesses 7-25 sigma, three cutoff radii, two temperatures): the root-mean-square residual is 0.001-0.002 epsilon/sigma^3, against 0.010-0.021 for the uncorrected profile, and Q, the amount that the contour choice transfers between the two interfaces of a film with non-equivalent surfaces, is recovered to within 0.6% of the surface tension. Applied to the normal component, the same closure removes 83-92% of the spurious structure of the per-atom zz profile, a test that needs no IK run. Its mixture form is validated on three two-component films with an adsorbate unequally distributed between their faces, where it resolves the tension of each face; a clean face recovers the tension of the pure film.
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BibTeX
@misc{rivera2026estimating,
title = {{Estimating Irving-Kirkwood pressure profiles from per-atom virial and density profiles: a closure for the contour-dependent term in planar liquid films}},
author = {Jose L. Rivera},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.41906},
eprint = {2610.41906},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.41906},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Estimating Irving-Kirkwood pressure profiles from per-atom virial and density profiles: a closure for the contour-dependent term in planar liquid films
AU - Jose L. Rivera
PY - 2026
DA - 2026/10/30
PB - arXiv
DO - 10.48550/arxiv.2610.41906
UR - https://arxiv.org/abs/2610.41906
AB - The local pressure tensor of an inhomogeneous fluid is not unique. Two tangential profiles are in common use in planar simulations: the Irving-Kirkwood (IK) profile, which requires a dedicated pass over every pair of atoms for every slab, and the per-atom virial (PAV) profile, which molecular-dynamics codes produce at negligible cost and coincides with the Harasima contour. The two differ by the derivative of a pair quantity, P_T^IK - P_T^PAV = dQ/dz. We show that, for Lennard-Jones free-standing films, Q(z) can be predicted from the density profile and the bulk radial distribution function of the coexisting liquid: under the closure rho2(r1,r2) ~ rho(z1) rho(z2) g(r12), with a pair-local interpolation of g between its liquid and dilute limits, Q is a double integral of rho(z) against a kernel built from u'(r) g(r). The estimator P_T^IK,est = P_T^PAV + dQ/dz is tested against IK profiles measured on the same trajectories for 20 films (thicknesses 7-25 sigma, three cutoff radii, two temperatures): the root-mean-square residual is 0.001-0.002 epsilon/sigma^3, against 0.010-0.021 for the uncorrected profile, and Q, the amount that the contour choice transfers between the two interfaces of a film with non-equivalent surfaces, is recovered to within 0.6% of the surface tension. Applied to the normal component, the same closure removes 83-92% of the spurious structure of the per-atom zz profile, a test that needs no IK run. Its mixture form is validated on three two-component films with an adsorbate unequally distributed between their faces, where it resolves the tension of each face; a clean face recovers the tension of the pure film.
ER -