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Effective three-body potentials for Li+(aq) and Mg2+(aq)
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
2003 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 119, no 14, 7263- p.Article in journal (Refereed) Published
Abstract [en]

A method for the extraction of effective three-body potential parameters from high-level ab initio cluster calculations is presented and compared to effective pair potentials extracted at the same level. Dilute Li+(aq) and Mg2+(aq) solutions are used as test cases and long molecular-dynamics simulations using these newly developed potentials were performed. Resulting thermodynamical, structural, and dynamical properties are compared to experiment as well as to the empirical effective pair potentials of Åqvist. Moreover, a new time-saving method for the correction of cluster energies computed with a relatively cheap ab initio method, to yield expensive, high-level ab initio energies, is presented. The effective pair approach is shown to give inconsistent results when compared to the effective three-body potentials. The performance of three different charge compensation methods (uniform charge plasm, Bogusz net charge correction, and counter ions) is compared for a large number of different system sizes. For most properties studied here, the system-size dependence is found to be small for system sizes with 256 water molecules or more. However, for the self-diffusion coefficients, a 1/L dependence is found, i.e., a very large system-size dependence. A very simple method for correcting for this deficiency is proposed. The results for most properties are found to compare reasonably well to experiment when using the effective three-body potentials.

Place, publisher, year, edition, pages
2003. Vol. 119, no 14, 7263- p.
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-46241DOI: 10.1063/1.1604372OAI: oai:DiVA.org:uu-46241DiVA: diva2:74149
Available from: 2006-03-21 Created: 2006-03-21 Last updated: 2017-12-05Bibliographically approved
In thesis
1. Cation Solvation in Water and Acetonitrile from Theoretical Calculations
Open this publication in new window or tab >>Cation Solvation in Water and Acetonitrile from Theoretical Calculations
2003 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Metal ions solvated in aqueous, non-aqueous, and mixtures of solvents occur in many chemical contexts, for example in electrochemical applications and solvent separation. Solvated ions appear in high concentration in the living organisms, where their presence or absence can fundamentally alter the functions of life. In many of these cases, understanding the selective solvation and the dynamics of the ions is essential for the understanding of the processes involved.

Computer simulation provides a molecular level of detail of the solvation process usually not available from experiments. The quality of the interaction models employed in the theoretical description is of particular importance, since even rather small changes in the interaction can lead to substantial and qualitative differences.

This thesis describes the development of a sequence of increasingly refined analytical ion-solvent potentials from ab initio calculations for the systems Li+(aq), Na+(aq), Mg2+(aq), Al3+(aq), Li+(MeCN), Na+(MeCN), Li+(aq, MeCN), and Na+(aq, MeCN). Molecular dynamics simulations using these potentials were subsequently performed, and some key-properties computed. The reliability of the computed thermodynamical, structural and dynamical properties was scrutinized.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2003. 45 p.
Series
Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1104-232X ; 892
Keyword
Inorganic chemistry, molecular dynamics, ab initio, lithium, sodium, magnesium, aluminum, metal ion, water, acetonitrile, solution, solvation, Oorganisk kemi
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-3598 (URN)91-554-5751-7 (ISBN)
Public defence
2003-10-24, 2001, The Ångström Laboratory, Uppsala, 10:15
Opponent
Supervisors
Available from: 2003-10-03 Created: 2003-10-03 Last updated: 2013-07-24Bibliographically approved

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Spångberg, DanielHermansson, Kersti

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