Sökning: onr:"swepub:oai:DiVA.org:uu-208355" >
Theoretical study o...
-
Barata-Morgado, Rute
(författare)
Theoretical study of the conformational equilibrium of 1,4-dioxane in gas phase, neat liquid, and dilute aqueous solutions
- Artikel/kapitelEngelska2013
Förlag, utgivningsår, omfång ...
-
2013-09-05
-
Springer Science and Business Media LLC,2013
-
printrdacarrier
Nummerbeteckningar
-
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
Kompletterande språkuppgifter
-
Språk:engelska
-
Sammanfattning på:engelska
Ingår i deldatabas
Klassifikation
-
Ämneskategori:ref swepub-contenttype
-
Ämneskategori:art swepub-publicationtype
Anmärkningar
-
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.
Ämnesord och genrebeteckningar
-
1
-
4-Dioxane
-
ASEP/MD
-
QM/MM
-
Conformational equilibrium
-
Solvent effect
Biuppslag (personer, institutioner, konferenser, titlar ...)
-
Luz Sanchez, M.
(författare)
-
Fernández Galván, IgnacioUppsala universitet,Teoretisk kemi(Swepub:uu)ignga749
(författare)
-
Corchado, Jose C.
(författare)
-
Elena Martin, M.
(författare)
-
Munoz-Losa, Aurora
(författare)
-
Aguilar, Manuel A.
(författare)
-
Uppsala universitetTeoretisk kemi
(creator_code:org_t)
Sammanhörande titlar
-
Ingår i:Theoretical Chemistry accounts: Springer Science and Business Media LLC132:10, s. 1390-1432-881X1432-2234
Internetlänk
Hitta via bibliotek
Till lärosätets databas