Analysis of probability of inserting a hard spherical particle with small diameter in hard-sphere fluid.
| Autor: | Davidchack RL; School of Computing and Mathematical Sciences, University of Leicester, Leicester LE1 7RH, United Kingdom., Elmajdoub AA; School of Computing and Mathematical Sciences, University of Leicester, Leicester LE1 7RH, United Kingdom., Laird BB; Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, USA.; Freiburg Institute for Advanced Studies, University of Freiburg, Albertstraße 19, 79104 Freiburg, Germany. |
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| Jazyk: | angličtina |
| Zdroj: | The Journal of chemical physics [J Chem Phys] 2023 Nov 14; Vol. 159 (18). |
| DOI: | 10.1063/5.0170928 |
| Abstrakt: | The probability of inserting, without overlap, a hard spherical particle of diameter σ in a hard-sphere fluid of diameter σ0 and packing fraction η determines its excess chemical potential at infinite dilution, μex(σ, η). In our previous work [R. L. Davidchack and B. B. Laird, J. Chem. Phys. 157, 074701 (2022)], we used Widom's particle insertion method within molecular dynamics simulations to obtain high precision results for μex(σ, η) with σ/σ0 ≤ 4 and η ≤ 0.5. In the current work, we investigate the behavior of this quantity at small σ. In particular, using the inclusion-exclusion principle, we relate the insertion probability to the hard-sphere fluid distribution functions and thus derive the higher-order terms in the Taylor expansion of μex(σ, η) at σ = 0. We also use direct evaluation of the excluded volume for pairs and triplets of hard spheres to obtain simulation results for μex(σ, η) at σ/σ0 ≤ 0.2247 that are of much higher precision than those obtained earlier with Widom's method. These results allow us to improve the quality of the small-σ correction in the empirical expression for μex(σ, η) presented in our previous work. (© 2023 Author(s). Published under an exclusive license by AIP Publishing.) |
| Databáze: | MEDLINE |
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