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• W1990799820 abstract "The frequency shift of an AZ two-atomic fragment upon molecule transfer from gas to solution or matrix is investigated. The nearest neighbour ligands are considered to form a cluster. The coupling of the νs(AZ) mode with the cluster low-frequency oscillators (νQ) is taken into account. One such oscillator can be the νσ(AZ…B) intermolecular stretching frequency oscillator in the H-bonded or charge transfer complex. A general expression for the νs(AZ) frequency shift (Δω) is obtained, which allows for both the usual van der Waals interaction and the (νs, νσ) and (νs, νQ) mode couplings. When the former prevails, the relative frequency shift Δω/ωf is invariant to the Z → Z* (e.g., H → D) isotopic substitution. When the mode coupling prevails, the quantity Δω/ω2f is invariant what is typical for H bonds. If the H-bonded or charge transfer complexes are absent, the frequency shift Δω is proportional to α(ϱAZ + ϱL)−6 where α is the polarizability of the ligand, ϱAZ and ϱL are the van der Waals radii of AZ and ligand, respectively. The additional νs(AH) frequency shift upon transfer of the AH…B complex from the gas to solution seems to be caused by (νs, νQ) mode coupling." @default.
• W1990799820 created "2016-06-24" @default.
• W1990799820 creator A5077756829 @default.
• W1990799820 date "1986-05-01" @default.
• W1990799820 modified "2023-09-23" @default.
• W1990799820 title "Van der Waals interaction and hydrogen bond effects on molecular vibrational frequencies" @default.
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• W1990799820 doi "https://doi.org/10.1016/0301-0104(86)85026-1" @default.
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