uu.seUppsala University Publications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Large polarization but small electron transfer for water around Al3+ in a highly hydrated crystal
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
2014 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 16, no 20, 9351-9363 p.Article in journal (Refereed) Published
Abstract [en]

Precise molecular-level information on the water molecule is precious, since it affects our interpretation of the role of water in a range of important applications of aqueous media. Here we propose that electronic structure calculations for highly hydrated crystals yield such information. Properties of nine structurally different water molecules (19 independent O center dot center dot center dot O hydrogen bonds) in the Al(NO3)(3) center dot 9H(2)O crystal have been calculated from DFT calculations. We combine the advantage of studying different water environments using one and the same compound and method (instead of comparing a set of independent experiments, each with its own set of errors) with the advantage of knowing the exact atomic positions, and the advantage of calculating properties that are difficult to extract from experiment. We find very large Wannier dipole moments for H2O molecules surrounding the cations: 4.0-4.3 D (compared to our calculated value of 1.83 D in the gas phase). These are induced by the ions and the H-bonds, while other water interactions and the relaxation of the internal water geometry in fact decrease the dipole moments. We find a good correlation between the water dipole moment and the O center dot center dot center dot O distances, and an even better (non-linear) correlation with the average electric field over the molecule. Literature simulation data for ionic aqueous solutions fit quite well with our crystalline `dipole moment vs. O center dot center dot center dot O distance' curve. The progression of the water and cation charges from ` small clusters double right arrow large clusters double right arrow the crystal' helps explain why the net charges on all the water molecules are so small in the crystal.

Place, publisher, year, edition, pages
2014. Vol. 16, no 20, 9351-9363 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-227586DOI: 10.1039/c3cp55358bISI: 000335818600018OAI: oai:DiVA.org:uu-227586DiVA: diva2:730422
Available from: 2014-06-27 Created: 2014-06-27 Last updated: 2017-12-05Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Authority records BETA

Mitev, Pavlin D.Eriksson, AndersHermansson, Kersti

Search in DiVA

By author/editor
Mitev, Pavlin D.Eriksson, AndersHermansson, Kersti
By organisation
Structural ChemistryDepartment of Chemistry - Ångström
In the same journal
Physical Chemistry, Chemical Physics - PCCP
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 752 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf