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.
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.
@article{Cazade_2015, title={Solvation of fluoro-acetonitrile in water by 2D-IR spectroscopy: A combined experimental-computational study}, volume={142}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.4916630}, DOI={10.1063/1.4916630}, number={21}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Cazade, Pierre-André and Tran, Halina and Bereau, Tristan and Das, Akshaya K. and Kläsi, Felix and Hamm, Peter and Meuwly, Markus}, year={2015}, month=apr }
