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,
doi = {10.1063/1.4916630},
url = {https://doi.org/10.1063%2F1.4916630},
year = 2015,
month = {jun},
publisher = {{AIP} Publishing},
volume = {142},
number = {21},
pages = {212415},
author = {Pierre-Andr{\'{e}} Cazade and Halina Tran and Tristan Bereau and Akshaya K. Das and Felix Kläsi and Peter Hamm and Markus Meuwly},
title = {Solvation of fluoro-acetonitrile in water by 2D-{IR} spectroscopy: A combined experimental-computational study},
journal = {The Journal of Chemical Physics}
}