Phase diagram of the hard-sphere potential model in three and four dimensions using a pseudo-hard-sphere potential
The hard-sphere potential has become a cornerstone in the study of both molecular and complex fluids. Despite its mathematical simplicity, its implementation in fixed time step molecular simulations remains a formidable challenge due to the discontinuity at contact. To avoid the issues associated with the ill-defined force at contact, a continuous potential has recently been proposed-here referred to as the pseudo-hard-sphere potential (pHS) [Báez et al., J. Chem, Phys. 149, 164907 (2018)]. This potential is constructed to match the second virial coefficient of the hard-sphere potential and is expected to mimic its thermodynamic properties. However, this hypothesis has only been partially validated within the fluid region of the phase diagram for hard-sphere dispersions in two and three dimensions. In this contribution, we examine the ability of the continuous pHS potential to reproduce the equation of state of a hard-sphere fluid, not only in the fluid phase but also across the fluid-solid coexistence region. Our focus is primarily on the phase diagram of hard-sphere systems in three and four dimensions; however, we also report on the feasibility of the pHS to reproduce the long time dynamics of a three-dimensional colloidal dispersion. We compare the thermodynamic properties obtained from Brownian dynamics simulations of the pHS potential with those derived from refined event-driven simulations of the corresponding hard-sphere potential. Furthermore, we provide a comparative analysis with theoretical equations of state based on both mean-field and integral equation approximations.
Authors
- Edwin A. Bedolla-Montiel (ORCID: https://orcid.org/0000-0002-7033-217X)
- Ramón Castañeda-Priego (ORCID: https://orcid.org/0000-0001-8115-9395)
- Ramón A. Castañeda-Cerdán
Institutions
- Universidad de Guanajuato (MX)
- Utrecht University (NL)
- Instituto Politécnico Nacional (MX)
- Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional (MX)
Publication Details
- Journal
- The Journal of Chemical Physics
- Published
- 2025-04-22
- DOI
- https://doi.org/10.1063/5.0264356
- Citations
- 2
- Primary Topic
- Phase Equilibria and Thermodynamics
- Type
- article
- Field-Weighted Citation Impact
- 1.35
Funders
- Fundación Marcos Moshinsky
- Consejo Nacional de Ciencia y Tecnología