ABSTRACT
The chemical pressure approach offers a new paradigm for property control in functional materials. In this work, we disclose a correlation between the ß â α pressure-induced phase transition in SnMoO4 and the substitution process of Mo6+ by W6+ in SnMo1-xWxO4 solid solutions (x = 0-1). Special attention is paid to discriminating the role of the lone pair Sn2+ cation from the structural distortive effect along the Mo/W substitution process, which is crucial to disentangle the driven force of the transition phase. Furthermore, the reverse α â ß transition observed at high temperature in SnWO4 is rationalized on the same basis as a negative pressure effect associated with a decreasing of W6+ percentage in the solid solution. This work opens a versatile chemical approach in which the types of interactions along the formation of solid solutions are clearly differentiated and can also be used to tune their properties, providing opportunities for the development of new materials.
ABSTRACT
We report here the analysis of vibrational properties of the sanbornite (low-BaSi2O5) and Ba5Si8O21 using theoretical and experimental approaches, as well as results of high temperature experiments up to 1100-1150 °C. The crystal parameters derived from Rietveld refinement and calculations show excellent agreement, within 4%, while the absolute mean difference between the theoretical and experimental results for the IR and Raman vibrational frequencies was <6 cm-1. The temperature-dependent Raman study renders that both sanbornite and Ba5Si8O21 display specific Ba and Si sites and their BaO and SiO bonds. In the case of the stretching modes assigned to specific Si sites, the frequency dependence on the SiO bond length exhibited very strong correlations. Both phases showed that for a change of 0.01 Å, the vibrational mode shifted 10 ± 2 cm-1. These results are promising for using Raman spectroscopy to track in situ reactions under a wide variety of conditions, especially during crystallization.
