Diffraction and spectroscopic studies of the cobaltic acid system HCoO 2-DCoO2

Robert G. Delaplane*, James A. Ibers, John R. Ferraro, John J. Rush

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

124 Scopus citations

Abstract

Cobaltic acid, HCoO2, and deuterated cobaltic acid, DCoO 2, have been prepared and studied by x-ray and neutron-diffraction techniques, and by infrared spectroscopy and cold-neutron scattering. The materials crystallize in apparent space group D3d5-R3m of the trigonal system with three molecules in a hexagonal cell of dimensions: HCoO2, a= 2.851(1), c=13.150(5) Å; DCo02, a=2.8S4(1), c= 13.354(5) Å. The O-O distance, as determined by neutron-powder studies, of HCoO2 is 2.50(2) Å. On this basis and the fact that there are three 0-H-O bonds along the c direction, the O-D-0 distance is 2.57 (2) Å. Hence, the isotope effect here is as large as in the system HCrO 2-DCrO2. Infrared studies at room temperature and at -195°C over the region 70-4000 cm-1 may be interpreted in terms of an effectively symmetric O-H-O bond and an effectively asymmetric O-D-O bond. Although the neutron inelastic scattering measurements are not inconsistent with this interpretation, there is a band centered at 264 cm"1 in the neutron spectrum for HCoO2, which is not observed in the infrared spectrum. Model calculations, based on a two-dimensional potential function in which the asymmetric stretching frequency is coupled to the symmetric stretching frequency, were unsuccessful owing to the magnitude of the coupling term required to account for the very large isotope effect.

Original languageEnglish (US)
Pages (from-to)1920-1927
Number of pages8
JournalThe Journal of Chemical Physics
Volume50
Issue number5
DOIs
StatePublished - Jan 1 1969

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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