Keywords
Kirkwood-Buff solution theory, molecular simulations
Abstract
Kirkwood-Buff (KB) solution theory is a means to obtain certain thermodynamic derivatives from knowledge of molecular distributions. In actual practice the required integrals over radial distribution functions suffer inaccuracies due to finite-distance truncation effects and their use in closed systems. In this work we discuss how best to minimize these inaccuracies under traditional KB theory. In addition we implement a method for calculating KB quantities in molecular simulations with periodic boundary conditions and particularly within the canonical ensemble. The method is based on a finite-Fourier-series expansion of molecular concentration fluctuations and leads to more reliable results for a given computational effort. The procedure is validated and compared to the original method for a nonideal liquid mixture of Lennard-Jones particles intended to imitate a real system, carbon tetrafluoride, and methane.
Original Publication Citation
Phys. Rev. E 80, 051203 – Published 23 November 2009. https://doi.org/10.1103/PhysRevE.80.051203
BYU ScholarsArchive Citation
Nichols, Joseph W.; Moore, Stan G.; and Wheeler, Dean R., "Improved implementation of Kirkwood-Buff solution theory in periodic molecular simulations" (2009). Faculty Publications. 6527.
https://scholarsarchive.byu.edu/facpub/6527
Document Type
Peer-Reviewed Article
Publication Date
2009-11-23
Publisher
American Physical Society
Language
English
College
Ira A. Fulton College of Engineering
Department
Chemical Engineering
Copyright Status
©2009 American Physical Society
Copyright Use Information
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