Alchemical free energy calculations via molecular dynamics have been applied to obtain thermodynamic properties related to solid–liquid equilibrium conditions, such as melting points. In recent years, the pseudo-supercritical path (PSCP) method has proved to be an important approach to melting point prediction due to its flexibility and applicability. In the present work, we propose improvements to the PSCP alchemical cycle to make it more compact and efficient through a concerted evaluation of different potential energies. The multistate Bennett acceptance ratio (MBAR) estimator was applied at all stages of the new cycle to provide greater accuracy and uniformity, which is essential concerning uncertainty calculations. In particular, for the multistate expansion stage from solid to liquid, we employed the MBAR estimator with a reduced energy function that allows affine transformations of coordinates. Free energy and mean derivative profiles were calculated at different cycle stages for argon, triazole, propenal, and the ionic liquid 1-ethyl-3-methyl-imidazolium hexafluorophosphate. Comparisons showed a better performance of the proposed method than the original PSCP cycle for systems with higher complexity, especially the ionic liquid. A detailed study of the expansion stage revealed that remapping the centers of mass of the molecules or ions is preferable to remapping the coordinates of each atom, yielding better overlap between adjacent states and improving the accuracy of the methodology.
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Revisiting the pseudo-supercritical path method: An improved formulation for the alchemical calculation of solid–liquid coexistence
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14 September 2023
Research Article|
September 11 2023
Revisiting the pseudo-supercritical path method: An improved formulation for the alchemical calculation of solid–liquid coexistence
Gabriela B. Correa
;
Gabriela B. Correa
(Investigation, Methodology, Software, Writing – original draft)
1
Chemical Engineering Program, Instituto Alberto Luiz Coimbra de Pós-Graduação e Pesquisa em Engenharia, Universidade Federal do Rio de Janeiro
, Rio de Janeiro RJ 21941-909, Brazil
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Yong Zhang
;
Yong Zhang
(Methodology, Software, Writing – review & editing)
2
Department of Chemical and Biomolecular Engineering, University of Notre Dame
, Notre Dame, Indiana 46556, USA
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Charlles R. A. Abreu
;
Charlles R. A. Abreu
(Conceptualization, Methodology, Supervision, Writing – review & editing)
3
Department of Chemical Engineering, Escola de Química, Universidade Federal do Rio de Janeiro
, Rio de Janeiro RJ 21941-909, Brazil
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Frederico W. Tavares
;
Frederico W. Tavares
a)
(Conceptualization, Formal analysis, Funding acquisition, Supervision, Writing – review & editing)
1
Chemical Engineering Program, Instituto Alberto Luiz Coimbra de Pós-Graduação e Pesquisa em Engenharia, Universidade Federal do Rio de Janeiro
, Rio de Janeiro RJ 21941-909, Brazil
3
Department of Chemical Engineering, Escola de Química, Universidade Federal do Rio de Janeiro
, Rio de Janeiro RJ 21941-909, Brazil
a)Author to whom correspondence should be addressed: tavares@eq.ufrj.br
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Edward J. Maginn
Edward J. Maginn
b)
(Conceptualization, Formal analysis, Funding acquisition, Supervision, Writing – review & editing)
2
Department of Chemical and Biomolecular Engineering, University of Notre Dame
, Notre Dame, Indiana 46556, USA
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a)Author to whom correspondence should be addressed: tavares@eq.ufrj.br
J. Chem. Phys. 159, 104105 (2023)
Article history
Received:
June 17 2023
Accepted:
August 16 2023
Citation
Gabriela B. Correa, Yong Zhang, Charlles R. A. Abreu, Frederico W. Tavares, Edward J. Maginn; Revisiting the pseudo-supercritical path method: An improved formulation for the alchemical calculation of solid–liquid coexistence. J. Chem. Phys. 14 September 2023; 159 (10): 104105. https://doi.org/10.1063/5.0163564
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