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Solvation of fluoro-acetonitrile in water by 2D-IR spectroscopy: A combined experimental-computational study.

  • Cazade PA Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland.
  • Tran H Department of Chemistry, University of Zurich, Winterthurerstr. 190, 8057 Zurich, Switzerland.
  • Bereau T Max-Planck-Institut für Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany.
  • Das AK Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland.
  • Kläsi F Department of Chemistry, University of Zurich, Winterthurerstr. 190, 8057 Zurich, Switzerland.
  • Hamm P Department of Chemistry, University of Zurich, Winterthurerstr. 190, 8057 Zurich, Switzerland.
  • Meuwly M Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland.
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  • 2015-06-08
Published in:
  • The Journal of chemical physics. - 2015
Acetonitriles
Hydrogen Bonding
Molecular Dynamics Simulation
Quantum Theory
Solubility
Spectrophotometry, Infrared
Water
English The solvent dynamics around fluorinated acetonitrile is characterized by 2-dimensional infrared spectroscopy and atomistic simulations. The lineshape of the linear infrared spectrum is better captured by semiempirical (density functional tight binding) mixed quantum mechanical/molecular mechanics simulations, whereas force field simulations with multipolar interactions yield lineshapes that are significantly too narrow. For the solvent dynamics, a relatively slow time scale of 2 ps is found from the experiments and supported by the mixed quantum mechanical/molecular mechanics simulations. With multipolar force fields fitted to the available thermodynamical data, the time scale is considerably faster--on the 0.5 ps time scale. The simulations provide evidence for a well established CF-HOH hydrogen bond (population of 25%) which is found from the radial distribution function g(r) from both, force field and quantum mechanics/molecular mechanics simulations.
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  • English
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green
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https://sonar.ch/global/documents/66282
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