Transfer of Protons through “Pure” Ice Ih Single Crystals. II. Molecular Models for Polarization and Conduction

Neither the polarization of pure ice single crystals can be understood on the basis of rotating H2O molecules nor the conduction through such crystals by assuming migrating H3O+ and OH− ions. Bjerrum's concepts of L‐, D‐defect and ionic‐defect formation are a useful starting point, but the subsequent development of double‐well models leads into serious difficulties. A new interpretation of the intrinsic polarization of ice Ih visualizes L, D pair formation as a one‐step process: a proton shifted by near‐infrared phonon excitation to an empty corner of its H2O tetrahedron. Subsequent intramolecular proton transfers, slightly field directed, inscribe a dipole moment into the disordered proton system of the ice crystal; the defects die off by recombination. Thus the polarization builds up from a statistically triggered pulse spectrum; its correlation period is the waiting time, until the same H2O molecule forms again a defect pair. This waiting period, the relaxation time of the Debye spectrum, connects the ...