The interpretation of vibrational spectra of ionic melts

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Abstract
Computer simulations of the short-time, vibrational dynamics of the network-forming ionic melts, LaCl 3 and ZnCl 2 , and of their mixtures with network-breaking alkali halides are described. In the mixtures, high frequency peaks in the vibrational density of states are shown to be describable in terms of the normal coordinates of vibration of transient molecular ion species, like LaCl 6 3− and ZnCl 4 2− . Novel simulation methods are presented which allow this association to be established. In the pure melts, the vibrational motions retain a strong aspect of this local polyhedral unit vibrational character, but the effects of network-induced coupling between the vibrations of different units become pronounced, particularly in ZnCl 2 . The calculated vibrational spectra are compared with extensive Raman data on these systems, and with infrared and neutronspectra in pure ZnCl 2 . For the mixtures, remarkably good agreement with experiment is found, confirming the high quality of the representation of the interionic interactions obtained with the polarizable ion model potentials used. For the melts, there are discrepancies between the peak frequencies observed in the vibrational DOS and the Raman spectra. These discrepancies are likely to be due to the network-induced couplings, whose effect on the Raman (and infrared) spectra is not fully included in the calculated DOS.