Fermi-Resonance Raman Spectra of Acetonitrile in Water and Water-Acetonitrile Mixture Solutions Based on the
Kayo Suda1, Kiyoshi Yagi2, Daisuke Yokogawa1
1Graduate School of Arts and Sciences, The University of Tokyo, 3-8-1, Komaba, Meguro-Ku, Tokyo153-8902, Japan.
Abstract:
We present an approach for calculating three-mode-coupling Fermi-resonance Raman spectra of acetonitrile molecules in solution by combining the Reference Interaction Site Model Self-Consistent Field method coupled with the constrained Spatial Electron Density Distribution (RISM-SCF-cSED) and second-order vibrational quasi-degenerate perturbation theory (VQDPT2). By describing solvents using integral equation theory and modeling anharmonic vibrations with VQDPT2, this method enables efficient computation of three-mode-coupling Fermi resonance Raman spectra of acetonitrile in solution at a modest computational cost. We demonstrate its application to acetonitrile in water and to acetonitrile-water mixture solutions, showing that the predicted peak positions and solvent-induced shifts in the Raman spectra agree well with experiment. Analysis of radial distribution functions indicates that the packing of water molecules around the cyano group of acetonitrile influences the nonlinear, high-frequency shift of its cyano stretching vibration in solution.
More Related Videos
09:57Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems
Published on: February 10, 2020
11:38In situ FTIR Spectroscopy as a Tool for Investigation of Gas/Solid Interaction: Water-Enhanced CO2 Adsorption in UiO-66 Metal-Organic Framework
Published on: February 1, 2020
Related Concept Videos
Raman Spectroscopy: Overview
However, a small fraction of the scattered light exhibits a frequency shift due to the exchange of energy between the incident photons and the...
IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations
IR Spectroscopy: Molecular Vibration Overview
Stretching vibrations are vibrational motions that occur along the bond line, changing the bond length or distance between two bonded atoms. They are further distinguished as symmetric or asymmetric. In symmetric stretching, the...
Spectroscopy of Carboxylic Acid Derivatives
In the...
¹H NMR Signal Integration: Overview
NMR Spectroscopy Of Amines
