: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Superionic conductors are compounds that exhibit exceptionally high values of ionic conductivity within the solid state. Indeed, their conductivities often reach values of the order of 1 Ω−1 cm−1, which are comparable to those observed in the molten state. Following Faraday's first observation of high ionic conductivity within the solids β-PbF2 and Ag2S in 1836, a fundamental understanding of the nature of the superionic state has provided one of the major challenges in the field of condensed matter science. However, experimental and theoretical approaches to their study are often made difficult by the extensive dynamic structural disorder which characterizes superionic conduction and the inapplicability of many of the commonly used approximations in solid state physics. Nevertheless, a clearer picture of the nature of the superionic state at the ionic level has emerged within the past few decades. Many different techniques have contributed to these advances, but the most significant insights have been provided by neutron scattering experiments and molecular dynamics simulations. This review will summarize the state of current knowledge concerning the crystal structures and conduction processes of superionic conductors, beginning with a comparison of the behaviour of two of the most widely studied binary compounds, AgI and β-PbF2. Each can be considered a parent of two larger families of highly conducting compounds which are related by either chemical or structural means. These include perovskite-structured oxides and Li+ containing spinel-structured compounds, which have important commercial applications in fuel cells and lightweight batteries, respectively. In parallel with these discussions, the relative importance of factors such as bonding character and the properties of the mobile and immobile ions (charge, size, polarizability, etc) in promoting the extensive lattice disorder which characterizes superionic behaviour will be assessed and the possibilities for predicting a priori which compounds will display high ionic conductivity discussed.

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Superionics: crystal structures and conduction processes

Experimental studies of structurally incommensurate crystal phases

Pressure induced amorphization of materials

Resonance Raman spectra are obtained when the wave number of the exciting radiation is close to, or coincident with, that of an electronic transition of the scattering species. Such spectra are usually characterized by a very large enhancement of the intensities of particular Raman bands, sometimes with the appearance of intense overtone and combination tone progressions. The technique provides detailed information about excited electronic states because it is only the vibrational modes associated with the chromophore that are resonance-Raman active. Additionally, the high sensitivity is such that compounds at concentrations as low as 10−6 mol/L may be detected, enabling resonance Raman spectroscopy to be used as an analytical tool and for the study of chromophores in molecules of biological interest.

Resonance Raman Spectroscopy, and Its Application to Inorganic Chemistry. New Analytical Methods (27)

Solid State Communications 112 (1999) 383–386

The vibrational properties of WO3 ceramics in the 30–300 K temperature range were probed by Raman spectroscopy. Starting with WO3 ceramics at room temperature presenting monoclinic (V) and triclinic (VI) mixed phases, structural transitions related to decreasing temperature were observed. At low temperatures a monoclinic (VII) and a new mixed phase were observed, the former characteristic of WO3 bulk and the latter associated to microcrystals. The analysis of the spectra indicated that the new phase develops gradually and it comes mainly from the monoclinic (V) phase. Copyright © 2001 John Wiley & Sons, Ltd.

Phase transition in WO3 microcrystals obtained by sintering process

High-pressure Raman spectra ofL-threonine crystal

http://repositorio.unicamp.br/jspui/bitstream/REPOSIP/98215/1/2-s2.0-0004029005.pdf

F. E. A. Melo

Papers

Solid State Communications 112 (1999) 383–386

Phase transition in WO3 microcrystals obtained by sintering process

High-pressure Raman spectra ofL-threonine crystal

Pressure-induced phase transitions in KLiSO4.

Pressure-induced phase transformations in l-alanine crystals