title: Solvation of fluoro-acetonitrile in water by 2D-IR spectroscopy: A combined experimental-computational study.
abstract: 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.affiliation: Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland.
authors.forename: Pierre-André
authors.initials: PA
authors.lastname: Cazade
authors.affiliation: Department of Chemistry, University of Zurich, Winterthurerstr. 190, 8057 Zurich, Switzerland.
authors.forename: Halina
authors.initials: H
authors.lastname: Tran
authors.affiliation: Max-Planck-Institut für Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany.
authors.forename: Tristan
authors.initials: T
authors.lastname: Bereau
authors.affiliation: Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland.
authors.forename: Akshaya K
authors.initials: AK
authors.lastname: Das
authors.affiliation: Department of Chemistry, University of Zurich, Winterthurerstr. 190, 8057 Zurich, Switzerland.
authors.forename: Felix
authors.initials: F
authors.lastname: Kläsi
authors.affiliation: Department of Chemistry, University of Zurich, Winterthurerstr. 190, 8057 Zurich, Switzerland.
authors.forename: Peter
authors.initials: P
authors.lastname: Hamm
authors.affiliation: Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland.
authors.forename: Markus
authors.initials: M
authors.lastname: Meuwly
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D006860:Hydrogen Bonding; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D012995:Solubility; D013055:Spectrophotometry, Infrared; D014867:Water / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D014867:Water