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Al3+, Ca2+, Mg2+, and Li+ in aqueous solution: Calculated first-shell anharmonic OH vibrations at 300 K
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Structural Chemistry.
2010 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 133, no 17, 174513- p.Article in journal (Refereed) Published
Abstract [en]

The anharmonic OH stretching vibrational frequencies, nu(OH), for the first-shell water molecules around the Li+, Ca2+, Mg2+, and Al3+ ions in dilute aqueous solutions have been calculated based on classical molecular dynamics (MD) simulations and quantum-mechanical (QM) calculations. For Li+(aq), Ca2+(aq), Mg2+(aq), and Al3+(aq), our calculated IR frequency shifts, Delta nu(OH), with respect to the gas-phase water frequency, are about -300, -350, -450, and -750 cm(-1), compared to -290, -290, -420, and -830 cm(-1) from experimental infrared (IR) studies. The agreement is thus quite good, except for the order between Li+ and Ca2+. Given that the polarizing field from the Ca2+ ion ought to be larger than that from Li+(aq), our calculated result seems reasonable. Also the absolute OH frequencies agree well with experiment. The method we used is a sequential four-step procedure: QM(electronic) to make a force field+MD simulation +QM(electronic) for point-charge-embedded Mn+ (H2O)(x)(first shell) (H2O)(y)(second shell) (H2O)(z)(third shell) clusters+QM(vibrational) to yield the OH spectrum. The many-body Ca2+-water force-field presented in this paper is new. IR intensity-weighting of the density-of-states frequency distributions was carried out by means of the squared dipole moment derivatives.

Place, publisher, year, edition, pages
2010. Vol. 133, no 17, 174513- p.
Keyword [en]
aluminium, calcium, infrared spectra, lithium, magnesium, molecular dynamics method, positive ions, solvation, solvent effects, vibrational states, water
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-135346DOI: 10.1063/1.3460261ISI: 000283936200059OAI: oai:DiVA.org:uu-135346DiVA: diva2:375468
Available from: 2010-12-08 Created: 2010-12-06 Last updated: 2017-12-11Bibliographically approved

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Spångberg, DanielHermansson, Kersti

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