Utility of chemical computations in predicting solution free energies of metal ions
Abstract
In this paper, we study quasi-chemical theory (QCT) for the free energies of divalent alkaline earth ions (Ba2+, Sr2+, Ca2+, Mg2+) in water, emphasizing that: (a) interactions between metal ions and proximal water molecules are as strong as traditional chemical effects; (b) QCT builds directly from accessible electronic structure calculations but rests on fully elaborated molecular statistical thermodynamics; (c) QCT offers choices of convenience in identifying coordination numbers for analysis. We investigate utilisation of direct QCT with inner-shell conditioning nλ=$$\overline{n}$$, alternative to the traditional nλ=0 conditioning motivated by a generalised van der Waals view. The alternative nλ=$$\overline{n}$$ works well: deleterious non-Gaussian effects of van der Waals repulsive interactions are not serious, and the alternative conditioning improves the convenience of QCT calculations. Additionally, comparison between ab initio and force field molecular dynamics (AIMD and FFMD) with standard models suggests that FFMD likely exaggerates the anharmonicity in the thermal motion of inner-shell ion-water clusters. Together with the general encouraging support for the harmonic approximations implied by the nλ=$$\overline{n}$$ conditioning, that observation helps explain the remarkable success of the cluster-based QCT solution free energies, which do not require assessment of all inner-shell occupancies by simulation.
- Authors:
-
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Tulane Univ., New Orleans, LA (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1485840
- Report Number(s):
- SAND-2018-11510J
Journal ID: ISSN 0892-7022; 669384
- Grant/Contract Number:
- AC04-94AL85000; AC02-05CH11231; AC52-06NA25396
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Molecular Simulation
- Additional Journal Information:
- Journal Volume: 44; Journal Issue: 2; Journal ID: ISSN 0892-7022
- Publisher:
- Taylor & Francis
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Quasi-chemical theory; ion solvation; ion channel blockers
Citation Formats
Chaudhari, Mangesh I., Pratt, Lawrence R., and Rempe, Susan B. Utility of chemical computations in predicting solution free energies of metal ions. United States: N. p., 2017.
Web. doi:10.1080/08927022.2017.1342127.
Chaudhari, Mangesh I., Pratt, Lawrence R., & Rempe, Susan B. Utility of chemical computations in predicting solution free energies of metal ions. United States. https://doi.org/10.1080/08927022.2017.1342127
Chaudhari, Mangesh I., Pratt, Lawrence R., and Rempe, Susan B. Sun .
"Utility of chemical computations in predicting solution free energies of metal ions". United States. https://doi.org/10.1080/08927022.2017.1342127. https://www.osti.gov/servlets/purl/1485840.
@article{osti_1485840,
title = {Utility of chemical computations in predicting solution free energies of metal ions},
author = {Chaudhari, Mangesh I. and Pratt, Lawrence R. and Rempe, Susan B.},
abstractNote = {In this paper, we study quasi-chemical theory (QCT) for the free energies of divalent alkaline earth ions (Ba2+, Sr2+, Ca2+, Mg2+) in water, emphasizing that: (a) interactions between metal ions and proximal water molecules are as strong as traditional chemical effects; (b) QCT builds directly from accessible electronic structure calculations but rests on fully elaborated molecular statistical thermodynamics; (c) QCT offers choices of convenience in identifying coordination numbers for analysis. We investigate utilisation of direct QCT with inner-shell conditioning nλ=$\overline{n}$, alternative to the traditional nλ=0 conditioning motivated by a generalised van der Waals view. The alternative nλ=$\overline{n}$ works well: deleterious non-Gaussian effects of van der Waals repulsive interactions are not serious, and the alternative conditioning improves the convenience of QCT calculations. Additionally, comparison between ab initio and force field molecular dynamics (AIMD and FFMD) with standard models suggests that FFMD likely exaggerates the anharmonicity in the thermal motion of inner-shell ion-water clusters. Together with the general encouraging support for the harmonic approximations implied by the nλ=$\overline{n}$ conditioning, that observation helps explain the remarkable success of the cluster-based QCT solution free energies, which do not require assessment of all inner-shell occupancies by simulation.},
doi = {10.1080/08927022.2017.1342127},
journal = {Molecular Simulation},
number = 2,
volume = 44,
place = {United States},
year = {Sun Jun 25 00:00:00 EDT 2017},
month = {Sun Jun 25 00:00:00 EDT 2017}
}
Web of Science
Figures / Tables:
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Figures / Tables found in this record: