Estimating the disjoining pressure of liquid nanofilms from molecular dynamics simulations via implicit treatment of the bulk liquid phase

Abstract

The commonly adopted constant bulk liquid density approximation for estimating disjoining pressure in liquid nanofilms, although justified by the low compressibility of liquids, can introduce significant errors in its evaluation. We hypothesize that the bulk liquid density is a thermodynamic state variable that depends on film thickness and local pressure, and should therefore be determined self-consistently to accurately capture interfacial forces under confinement. A thermodynamically consistent molecular dynamics simulation framework is developed by coupling a surface-tension-based formulation with bulk equations of state obtained from independent simulations. An iterative algorithm is employed to simultaneously determine bulk liquid density, film thickness, and disjoining pressure. The method is applied to water and argon nanofilms, and results are benchmarked against conventional constant-density approaches and alternative computational routes based on chemical potential calculation. The proposed framework provides a computationally efficient and thermodynamically rigorous route for evaluating disjoining pressure without requiring explicit full coexisting system simulations. Incorporating density variations significantly improves the accuracy and consistency of predicted disjoining pressures. For water nanofilms, a 3.6% deviation in density can lead to up to 77% overestimation of disjoining pressure at a thickness of 12 Å, whereas the effect is weaker but still non-negligible for argon. The proposed framework restores the inverse-cubic scaling with film thickness predicted by Hamaker theory and reduces discrepancies between independent computational methods. Overall, the results demonstrate that self-consistent treatment of bulk thermodynamics is essential for quantitatively reliable evaluation of surface forces in confined fluid systems.