Abstract
The van der Waals interaction free energy Aint between two spherical bodies of Stockmayer fluid across a
vacuum is calculated using molecular simulations and classical perturbation theory. The results are decomposed
into their electrostatic and Lennard-Jones parts, and the former is shown to agree excellently with predictions from
dielectric continuum theory. Aint is decomposed into its energetic and entropic contributions and the results are
compared with analytical predictions. Finally, we expand the electrostatic part of Aint in a multipole expansion,
and show that the surprisingly good agreement between the molecular and continuum descriptions is likely due to
a cancellation of errors coming from the neglect of the discrete nature of the fluid within the dielectric description.
vacuum is calculated using molecular simulations and classical perturbation theory. The results are decomposed
into their electrostatic and Lennard-Jones parts, and the former is shown to agree excellently with predictions from
dielectric continuum theory. Aint is decomposed into its energetic and entropic contributions and the results are
compared with analytical predictions. Finally, we expand the electrostatic part of Aint in a multipole expansion,
and show that the surprisingly good agreement between the molecular and continuum descriptions is likely due to
a cancellation of errors coming from the neglect of the discrete nature of the fluid within the dielectric description.
Original language | English |
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Article number | 011117 |
Journal | Physical Review E (Statistical, Nonlinear, and Soft Matter Physics) |
Volume | 84 |
Issue number | 1 |
DOIs | |
Publication status | Published - 2011 |
Bibliographical note
The information about affiliations in this record was updated in December 2015.The record was previously connected to the following departments: Physical Chemistry 1 (S) (011001006), Theoretical Chemistry (S) (011001039)
Subject classification (UKÄ)
- Theoretical Chemistry
- Physical Chemistry