TY - JOUR
T1 - Solvation of fluoro-acetonitrile in water by 2D-IR spectroscopy
T2 - A combined experimental-computational study
AU - Cazade, Pierre André
AU - Tran, Halina
AU - Bereau, Tristan
AU - Das, Akshaya K.
AU - Kläsi, Felix
AU - Hamm, Peter
AU - Meuwly, Markus
N1 - Publisher Copyright:
© 2015 AIP Publishing LLC.
PY - 2015/6/7
Y1 - 2015/6/7
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84965093621&partnerID=8YFLogxK
U2 - 10.1063/1.4916630
DO - 10.1063/1.4916630
M3 - Article
C2 - 26049435
AN - SCOPUS:84965093621
SN - 0021-9606
VL - 142
SP - 212415
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 21
M1 - 212415
ER -