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

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.
Authors:
;  [1] ; ; ;  [2] ;  [3] ;  [1] ;  [4]
  1. Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel (Switzerland)
  2. Department of Chemistry, University of Zurich, Winterthurerstr. 190, 8057 Zurich (Switzerland)
  3. Max-Planck-Institut für Polymerforschung, Ackermannweg 10, 55128 Mainz (Germany)
  4. (United States)
Publication Date:
OSTI Identifier:
22415894
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 21; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; ACETONITRILE; COMPUTERIZED SIMULATION; DENSITY FUNCTIONAL METHOD; HYDROGEN; INFRARED SPECTRA; QUANTUM MECHANICS; SOLVATION; SOLVENTS; SPATIAL DISTRIBUTION; TWO-DIMENSIONAL SYSTEMS; WATER