Vibrational band hydrogen bond polarization

In Section VI we study in detail two fast short-lived vibration mechanisms b and c, which concern item 2. The dielectric response to the elastic rotational vibrations of hydrogen-bonded (HB) polar molecules and to translational vibrations of charges, formed on these molecules, is revealed in terms of two interrelated Lorentz lines. A proper force constant corresponds to each line. The effect of these constants on the spectra of the complex susceptibility is considered. The dielectric response of the H-bonded molecules to elastic vibrations is shown to arise in the far IR region. Namely, the translational band (T-band) at the frequency v about 200 cm-1 is caused by vibration of charges, while the neighboring V-band at v about 150 cm-1 arises due to elastic rigid-dipole reorientations. In the case of water these bands overlap, and in the case of ice they are resolved due to longer vibration lifetime. 

Closing naphthyl ring. The induced dipole moment is then chirally disposed in relation to the inducing NH2 dipole moment. This mechanism, referred to as the dynamic polarization model (45), is shown to explain most of the observed VCD intensity in the synunetric NH2 stretching mode, >>nh2- The anisotropy ratio for this VCD band is ca. 10. Since an NH. . . x type hydrogen bond is possible in this molecule, a description based on vibrationally induced charge flow (currents) may also be riuitfiil, similar to that proposed for a-phenyleth-ylamine. Sect. FV-B-2. 

Section VI. It is possible to unblock the first drawback (i), if to assume a nonrigidity of a dipole—that is, to propose a polarization model of water. This generalization roughly takes into account specific interactions in water, which govern hydrogen-bond vibrations. The latter determine the absorption R-band in the vicinity of 200 cm-1. A simple modification of the hat-curved model is described, in which a dipole moment of a water molecule is represented as a sum of the constant (p) and of a small quasi-harmonic time-varying part p(/j. 

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