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  • Barata-Morgado, Rute (author)

Theoretical study of the conformational equilibrium of 1,4-dioxane in gas phase, neat liquid, and dilute aqueous solutions

  • Article/chapterEnglish2013

Publisher, publication year, extent ...

  • 2013-09-05
  • Springer Science and Business Media LLC,2013
  • printrdacarrier

Numbers

  • LIBRIS-ID:oai:DiVA.org:uu-208355
  • https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-208355URI
  • https://doi.org/10.1007/s00214-013-1390-4DOI

Supplementary language notes

  • Language:English
  • Summary in:English

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Classification

  • Subject category:ref swepub-contenttype
  • Subject category:art swepub-publicationtype

Notes

  • The conformational equilibrium of 1,4-dioxane in the gas phase, in the pure liquid, and in aqueous solution has been studied by means of the Average Solvent Electrostatic Potential from Molecular Dynamics (ASEP/MD) method and the Integral Equation Formalism for the Polarizable Continuum Model (IEF-PCM). The dioxane molecule was described at the DFT(B3LYP)/aug-cc-pVTZ level. In the three phases, the equilibrium is almost completely shifted toward the chair conformer, with populations of the twist-boat conformers lower than 0.01 %. The equilibrium is dominated by the internal energy of the molecule, as the solute-solvent interaction free energies are very similar in the three conformers considered (chair, 1,4 twist-boat, and 2,5 twist-boat). In the pure liquid, where the dioxane-dioxane interaction is dominated by the Lennard-Jones term, the structure is characteristic of a van der Waals liquid. However, the decrease in the C-H distance from gas phase to solution, the increase in the C-H vibrational frequencies, and the presence of a shoulder in the O-Haxial pair radial distribution function point to the presence of a weak C-H-O hydrogen bond. The analysis of the occupancy maps of water oxygen and hydrogen atoms around the 1,4-dioxane molecule confirms this conclusion. Contrary to what is found in small water-dioxane clusters, in the liquid, there is a preference for oxygen atoms to interact with axial hydrogen atoms to form C-H-O hydrogen bonds. Comparison of ASEP/MD and IEF-PCM results indicates that including specific interactions is very important for an adequate description of the solute-solvent interaction; however, the influence of these interactions does not translate in changes in the relative stability of the conformers because it cancels out when energy differences are calculated.

Subject headings and genre

  • 1
  • 4-Dioxane
  • ASEP/MD
  • QM/MM
  • Conformational equilibrium
  • Solvent effect

Added entries (persons, corporate bodies, meetings, titles ...)

  • Luz Sanchez, M. (author)
  • Fernández Galván, IgnacioUppsala universitet,Teoretisk kemi(Swepub:uu)ignga749 (author)
  • Corchado, Jose C. (author)
  • Elena Martin, M. (author)
  • Munoz-Losa, Aurora (author)
  • Aguilar, Manuel A. (author)
  • Uppsala universitetTeoretisk kemi (creator_code:org_t)

Related titles

  • In:Theoretical Chemistry accounts: Springer Science and Business Media LLC132:10, s. 1390-1432-881X1432-2234

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