The numerical computation of chemical potential in dense non-homogeneous fluids is a key problem in the study of confined fluid thermodynamics. To this day, several methods have been proposed; however, there is still need for a robust technique, capable of obtaining accurate estimates at large average densities. A widely established technique is the Widom insertion method, which computes the chemical potential by sampling the energy of insertion of a test particle. Non-homogeneity is accounted for by assigning a density dependent weight to the insertion points. However, in dense systems, the poor sampling of the insertion energy is a source of inefficiency, hampering a reliable convergence. We have recently presented a new technique for the chemical potential calculation in homogeneous fluids. This novel method enhances the sampling of the insertion energy via well-tempered metadynamics, reaching accurate estimates at very large densities. In this paper, we extend the technique to the case of non-homogeneous fluids. The method is successfully tested on a confined Lennard-Jones fluid. In particular, we show that, thanks to the improved sampling, our technique does not suffer from a systematic error that affects the classic Widom method for non-homogeneous fluids, providing a precise and accurate result.
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21 August 2018
Research Article|
May 07 2018
Chemical potential calculations in non-homogeneous liquids Available to Purchase
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Claudio Perego
;
Claudio Perego
a)
1
Department of Polymer Theory, Max-Planck Institute for Polymer Research
, Ackermannweg 10, D-55128 Mainz, Germany
2
Department of Chemistry and Applied Biosciences, ETH Zurich, c/o USI Campus
, Via Giuseppe Buffi 13, CH-6900 Lugano, Switzerland
3
Institute of Computational Science, National Center for Computational Design and Discovery of Novel Materials MARVEL, Università della Svizzera italiana
, Via Giuseppe Buffi 13, CH-6900 Lugano, Switzerland
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Omar Valsson
;
Omar Valsson
1
Department of Polymer Theory, Max-Planck Institute for Polymer Research
, Ackermannweg 10, D-55128 Mainz, Germany
2
Department of Chemistry and Applied Biosciences, ETH Zurich, c/o USI Campus
, Via Giuseppe Buffi 13, CH-6900 Lugano, Switzerland
3
Institute of Computational Science, National Center for Computational Design and Discovery of Novel Materials MARVEL, Università della Svizzera italiana
, Via Giuseppe Buffi 13, CH-6900 Lugano, Switzerland
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Michele Parrinello
Michele Parrinello
2
Department of Chemistry and Applied Biosciences, ETH Zurich, c/o USI Campus
, Via Giuseppe Buffi 13, CH-6900 Lugano, Switzerland
3
Institute of Computational Science, National Center for Computational Design and Discovery of Novel Materials MARVEL, Università della Svizzera italiana
, Via Giuseppe Buffi 13, CH-6900 Lugano, Switzerland
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Claudio Perego
1,2,3,a)
Omar Valsson
1,2,3
Michele Parrinello
2,3
1
Department of Polymer Theory, Max-Planck Institute for Polymer Research
, Ackermannweg 10, D-55128 Mainz, Germany
2
Department of Chemistry and Applied Biosciences, ETH Zurich, c/o USI Campus
, Via Giuseppe Buffi 13, CH-6900 Lugano, Switzerland
3
Institute of Computational Science, National Center for Computational Design and Discovery of Novel Materials MARVEL, Università della Svizzera italiana
, Via Giuseppe Buffi 13, CH-6900 Lugano, Switzerland
J. Chem. Phys. 149, 072305 (2018)
Article history
Received:
February 02 2018
Accepted:
February 21 2018
Citation
Claudio Perego, Omar Valsson, Michele Parrinello; Chemical potential calculations in non-homogeneous liquids. J. Chem. Phys. 21 August 2018; 149 (7): 072305. https://doi.org/10.1063/1.5024631
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