Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 115, Issue 44, Pages 12150-12160Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp206073v
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This article focuses on the problem of remarkably strong changes in the fine structure patterns of the v(N-H) and v(N-D) bands attributed to the hydrogen and deuterium bonds accompanying the phase transition, which occurs between two polymorphic forms of oxindole. The lattices of these two different crystals contain hydrogen-bonded cyclic dimers differ in their geometry parameters. The source of these differences in the polymorph spectral properties results from the geometry relations concerning the dimers constituting the lattice structural units. In the case of the alpha phase, the hydrogen bond lengths of the dimers differ by 0.18 angstrom. This leads to the off-resonance exciton coupling weakly involving the dimer hydrogen bonds. For the beta phase, with practically symmetric dimers in the lattice, the spectra become typical for centrosymmetric hydrogen bond systems due to the full resonance of the proton or deuteron vibrations.
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