Solvation of fluoro-acetonitrile in water by 2D-IR spectroscopy: A combined experimental-computational study
- Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel (Switzerland)
- Department of Chemistry, University of Zurich, Winterthurerstr. 190, 8057 Zurich (Switzerland)
- Max-Planck-Institut für Polymerforschung, Ackermannweg 10, 55128 Mainz (Germany)
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.
- OSTI ID:
- 22415894
- Journal Information:
- Journal of Chemical Physics, Vol. 142, Issue 21; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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