Raman spectroscopic study of hydrogen ordered ice XIII and of its reversible phase transition to disordered ice V

Abstract

Raman spectra of recovered ordered H₂O (D₂O) ice XIII doped with 0.01 M HCl (DCl) recorded in vacuo at 80 K are reported in the range 3600–200 cm⁻¹. The bands are assigned to the various types of modes on the basis of isotope ratios. On thermal cycling between 80 and 120 K, the reversible phase transition to disordered ice V is observed. The remarkable effect of HCl (DCl) on orientational ordering in ice V and its phase transition to ordered ice XIII, first reported in a powder neutron diffraction study of DCl doped D₂O ice V (C. G. Salzmann, P. G. Radaelli, A. Hallbrucker, E. Mayer, J. L. Finney, Science, 2006, 311, 1758), is demonstrated by Raman spectroscopy and discussed. The dopants KOH and HF have only a minor effect on hydrogen ordering in ice V, as shown by the Raman spectra.