A theoretical study of the OH stretching region of the vibrational spectrum of ice Ih
- 15 October 1978
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 69 (8) , 3483-3496
- https://doi.org/10.1063/1.437081
Abstract
We describe a theoretical interpretation of the OH stretching region of the vibrational spectrum of ice Ih derived from a study of extended models. The principle conclusions are the following: (i) The breadth and distribution of vibrational modes, and of intensity in the Raman and infrared spectra, are dominated by the influence of strong intermolecular coupling. The intermolecular coupling is comparable in strength to the intramolecular coupling. Long range couplings between molecules not directly hydrogen bonded mainly serve to make the features of the spectrum more diffuse than they would otherwise be, but have no great influence on the spectral distribution. (ii) The intramolecular OH stretch‐OH stretch coupling in ice Ih is of opposite sign to that in the gas phase. (iii) The vibrational modes of ice Ih are found to be complex mixtures of molecular motions, so identification of regions of the Raman or infrared spectra with particular isolated molecule modes is not useful. Rather good agreement is obtained between the Raman and infrared spectra predicted and those observed. Some deficiencies of the model, associated with residual discrepancies between theory and experiment, are discussed.Keywords
This publication has 20 references indexed in Scilit:
- The 2500–4000 cm−1 Raman and infrared spectra of low density amorphous solid water and of polycrystalline ice IChemical Physics Letters, 1977
- Vibrational spectra and topological structure of tetrahedrally bonded amorphous semiconductorsPhilosophical Magazine, 1976
- The overtone spectra of H2O, D2O and mixtures of H2O in D2O iceChemical Physics Letters, 1975
- Electronic structure based on the local atomic environment for tight-binding bands. IIJournal of Physics C: Solid State Physics, 1975
- Model calculation of the intramolecular vibration spectrum of liquid waterJournal of the American Chemical Society, 1974
- Electronic structure based on the local atomic environment for tight-binding bandsJournal of Physics C: Solid State Physics, 1972
- Infrared intensities of the stretching and librational bands of H2O, D2O, and HDO in solidsSpectrochimica Acta Part A: Molecular Spectroscopy, 1968
- Inter- and Intramolecular Potentials and the Spectrum of IceThe Journal of Chemical Physics, 1960
- Intensities in Raman spectra I. A bond polarizability theoryProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1953
- The Raman Spectrum and the Structure of WaterJournal of the American Chemical Society, 1937