Two-Dimensional Adiabatic Model for Calculating Progressions Resulting from Stretch-Rock Coupling in Vibrational
Elva V Henderson1, Kenneth D Jordan1
1Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
Abstract:
Several anion-water dimers feature a distinct progression in the OH stretch region of their vibrational spectra. This progression arises from strong anharmonic couplings between the OH stretch and low-frequency intermolecular modes. In this work, we introduce a two-dimensional adiabatic model accounting explicitly for the water and anion rock degrees of freedom and use it to calculate the vibrational spectra of HCO2-·(H2O) and NO3-·(H2O). The spectra calculated by using this model are in excellent agreement with experiment, in terms of both peak spacings and lengths of the progressions, and represent a substantial improvement over earlier models.
More Related Videos
Related Concept Videos
IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration
According to Hooke's law, the vibrational frequency is directly proportional to...
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...
IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations
IR Frequency Region: X–H Stretching
IR Frequency Region: Alkyne and Nitrile Stretching
Comparing the stretching vibrational frequency of C≡C triple bonds with that of double and single bonds, it is evident that C≡C triple bonds exhibit a higher stretching frequency than C=C double and C–C single bonds. Similarly, the C≡N triple bond...
¹H NMR: Interpreting Distorted and Overlapping Signals
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are...


