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Interactions and dynamics of small molecules in liquid mixtures: as studied by nuclear spin relaxation and computer simulations
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry, Physical Chemistry.
1990 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The present thesis concerns the interactions and dynamics of various types of smallmolecules in their liquid mixtures. The relationship between nuclear magneticrelaxation experiments, Molecular Dynamics simulations and dynamic models isexplored.Multinuclear magnetic relaxation was determined over the whole concentration rangein the components of the following binary mixtures: D^)-DMSO-dg, CD3CN-CDCI3 andCH3CN-H2O. Carbon-13 relaxation was measured in 1 mol% of sucrose and amethylated disaccharide in a 2:1 mixture of D2O-DMSO-dg, at variable temperatureoutside the extreme narrowing region. Nitrogen-14 relaxation was measured in 1 mol%of CHgCN in ^O-CHglCHg^OH as a function of the solvent mixture composition. Therotational correlation times were deduced from the relaxation rates. Self-diffusioncoefficients were also reported for the components of the CD3CN-CDCI3 system.Computer simulations were performed using the Molecular Dynamics method, and datacollected for the binary mixtures of CHgCN-CHClj and CH3CN-H2O over the wholeconcentration range. Radial distribution functions, pairwise interaction energies, andtime autocorrelation functions for the linear velocity, angular velocity andreorientation were reported.The NMR and MD-simulations data are not only directly compared, they are also usedto evaluate the applicability of diverse motional models. If a linear correlation withviscosity exists, the macroscopic hydrodynamic model is tested, possibly whileincluding some corrections for the molecular shape and boundary. However, this modelis seldom even seemingly correct for the small molecules of the present studies. Thediffusion model, where small angular displacements are assumed, is qualitativelyadequate in many cases. Nevertheless, some of the rotations are shown to be too far in theinertial limit to follow the diffusion model. The extended diffusion model, although itallows for rotations of arbitrary size, fails to describe the rotational motions in theacetonitrile/chloroform mixtures. The overall and internal motions of the twodisaccharides are described by the rotational diffusion model. A tentative attempt ismade to apply the continuum model of dielectric friction to acetonitrile in the mixedsolvent of water and 1-propanol.

Place, publisher, year, edition, pages
Stockholm: Stockholm University, 1990. , p. 50
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-164615Libris ID: 7608846ISBN: 91-7146-822-6 (print)OAI: oai:DiVA.org:su-164615DiVA, id: diva2:1279786
Public defence
1990-05-18, Hörsal G, Biologihusen, Frescati, Stockholm, 10:00
Note

Härtill 7 uppsatser

Available from: 2019-01-17 Created: 2019-01-17 Last updated: 2020-03-31Bibliographically approved

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