Assessing the Effect of Hofmeister Anions on the Hydrogen-Bonding Strength of Water via Nitrile Stretching Frequency Shift. Arusha Acharyya, Debopreeti Mukherjee, Feng Gai.The Journal of Physical Chemistry B 2021, 125 Changing Vibration Coupling Strengths of Liquid Acetonitrile with an Angle-Tuned Etalon. M←NCCH3, M-η2-(NC)–CH3, and CN–M–CH3 Prepared by Reactions of Ce, Sm, Eu, and Lu Atoms with Acetonitrile: Matrix Infrared Spectra and Theoretical Calculations. Fei Cong, Juanjuan Cheng, Han-Gook Cho, Tengfei Huang, Xuefeng Wang, Lester Andrews.TfNN15N: A γ-15N-Labeled Diazo-Transfer Reagent for the Synthesis of β-15N-Labeled Azides. Hyeok-Jun Kwon, Sungduk Gwak, Jun Young Park, Minhaeng Cho, Hogyu Han.The Journal of Physical Chemistry B 2022, 126 Characterization of Acetonitrile Isotopologues as Vibrational Probes of Electrolytes. Journal of the American Chemical Society 2022, 144 Nitrile Infrared Intensities Characterize Electric Fields and Hydrogen Bonding in Protic, Aprotic, and Protein Environments. Jared Bryce Weaver, Jacek Kozuch, Jacob M.Structure, Organization, and Heterogeneity of Water-Containing Deep Eutectic Solvents. Kai Töpfer, Andrea Pasti, Anuradha Das, Seyedeh Maryam Salehi, Luis Itza Vazquez-Salazar, David Rohrbach, Thomas Feurer, Peter Hamm, Markus Meuwly.
This article is cited by 221 publications. Although such theories are still in their infancy, we suggest that microheterogeneity could also account for most known properties of acetonitrile−alcohol solutions and, in fact, be a quite general phenomenon. Also, we measure Δν for acetonitrile in aqueous solution using Fourier transform Raman spectroscopy and show that the results are consistent with, but require modification of, microheterogeneity theories for the structure of acetonitrile−water solutions. The results are then convolved using known structural properties of the various solutions and/or related neat liquids, leading to an interpretation of the observed solvent shifts. To interpret this specific solvation, 95 MP2 or B3LYP calculations are performed to evaluate structures and CN frequency shifts for CH 3CN complexed with one molecule of either water, methanol, ethanol, 2-propanol, tert-butyl alcohol, phenol, benzyl alcohol, acetic acid, trifluoroacetic acid, 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, acetonitrile, chloroform, carbon tetrachloride, tetrahydrofuran, formamide, pyridine, or Cl -, as well as 45 parallel calculations for the solvent monomers or dimers. First, Δν is analyzed in terms of solvent repulsive and dielectric effects combined with specific solvation effects. We ascertain the robust features of these models and combine them into a new one in which solvent−solvent and solvent−solute forces compete to determine the structure of the solution and hence Δν.
The two major models (dispersive and specific solvation) which have been proposed to interpret Δν are based on diverse experiments with incompatible conclusions. We consider the properties of acetonitrile dissolved in 33 solvents, focusing on interpretation of the environment-sensitive solvent shift, Δν, of its CN stretch frequency, ν 2.
Despite this, we have no general picture of the nature of mixed liquids containing acetonitrile applicable across-solvent families. Acetonitrile is an extremely important solvent and cosolvent.
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