Počet záznamů: 1
Chemical Potentials, Activity Coefficients, and Solubility in Aqueous NaCl Solutions: Prediction by Polarizable Force Fields.
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SYSNO ASEP 0472724 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Chemical Potentials, Activity Coefficients, and Solubility in Aqueous NaCl Solutions: Prediction by Polarizable Force Fields. Tvůrce(i) Moučka, F. (CZ)
Nezbeda, Ivo (UCHP-M) RID, ORCID, SAI
Smith, W.R. (CA)Zdroj.dok. Journal of Chemical Theory and Computation . - : American Chemical Society - ISSN 1549-9618
Roč. 11, č. 4 (2015), s. 1756-1764Poč.str. 9 s. Jazyk dok. eng - angličtina Země vyd. US - Spojené státy americké Klíč. slova monte-carlo simulations ; molecular-dynamic simulations ; free-energy Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry Způsob publikování Omezený přístup Institucionální podpora UCHP-M - RVO:67985858 UT WOS 000353176500043 EID SCOPUS 84927916969 DOI https://doi.org/10.1021/acs.jctc.5b00018 Anotace We describe a computationally efficient molecular simulation methodology for calculating the concentration dependence of the chemical potentials of both solute and solvent in aqueous electrolyte solutions, based on simulations of the salt chemical potential alone. We use our approach to study the predictions for aqueous NaCl solutions at ambient conditions of these properties by the recently developed polarizable force fields (FFs) and by the nonpolarizable JC FF of Joung and Cheatham tailored to SPC/E water. We also consider their predictions of the concentration dependence of the electrolyte activity coefficient, the crystalline solid chemical potential, the electrolyte solubility, and the solution specific volume. We first highlight the disagreement in the literature concerning calculations of solubility by means of molecular simulation in the case of the JC FF and provide strong evidence of the correctness of our methodology based on recent independently obtained results for this important test case. We then compare the predictions of the three FFs with each other and with experiment and draw conclusions concerning their relative merits, with particular emphasis on the salt chemical potential and activity coefficient vs concentration curves and their derivatives. The latter curves have only previously been available from KirkwoodBuff integrals, which require approximate numerical integrations over system pair correlation functions at each concentration. Unlike the case of the other FFs, the AH/BK3 curves are nearly parallel to the corresponding experimental curves at moderate and higher concentrations. This leads to an excellent prediction of the water chemical potential via the GibbsDuhem equation and enables the activity coefficient curve to be brought into excellent agreement with experiment by incorporating an appropriate value of the standard state chemical potential in the Henry Law convention. Pracoviště Ústav chemických procesů Kontakt Eva Jirsová, jirsova@icpf.cas.cz, Tel.: 220 390 227 Rok sběru 2020 Elektronická adresa https://pubs.acs.org/doi/pdf/10.1021/acs.jctc.5b00018
Počet záznamů: 1