Behavior of Long-Chain Hydrocarbons at High Pressures and Temperatures.

Although long-chain aliphatic hydrocarbons are documented in meteorites, their origin is poorly understood. A key question is whether they are pristine or a byproduct of terrestrial alteration? To understand if these long-chain hydrocarbons are indigenous, it will be important to explore their thermodynamic and mechanical stability at conditions experienced by extraterrestrial objects during atmospheric entry and passage. Extreme pressures and temperatures experienced by meteorites are likely to alter the molecular organization of these long-chain hydrocarbons. These structural changes associated with extreme conditions are often documented via laboratory-based Raman spectroscopic measurements. So far, Raman spectroscopic measurements have investigated the effect of static compression on the aliphatic hydrocarbons. The effect of temperature on the structural changes remains poorly explored. To bridge this gap, in this study, we have explored the behavior of two aliphatic hydrocarbons at simultaneously high pressures and temperatures. We have used a resistively heated diamond anvil cell. On compression to moderate pressures, the appearance of new vibrational modes in the low-energy region confirms prior studies and is related to the bending of the linear chains. Upon heating to ∼220 °C, we note that the new low-energy mode undergoes softening. The mode softening is likely due to the combination of unbending of the alkane chain and mode anharmonicity.

Studies of Multiferroic Palladium Perovskites.

We have studied the atomic force microscopy (AFM), X-ray Bragg reflections, X-ray absorption spectra (XAS) of the Pd L-edge, Scanning electron microscopey (SEM) and Raman spectra, and direct magnetoelectric tensor of Pd-substituted lead titanate and lead zirconate-titanate. A primary aim is to determine the percentage of Pd+4 and Pd+2 substitutional at the Ti-sites (we find that it is almost fully substitutional). The atomic force microscopy data uniquely reveal a surprise: both threefold vertical (polarized out-of-plane) and fourfold in-plane domain vertices. This is discussed in terms of the general rules for Voronoi patterns (Dirichlet tessellations) in two and three dimensions. At high pressures Raman soft modes are observed, as in pure lead titanate, and X-ray diffraction (XRD) indicates a nearly second-order displacive phase transition. However, two or three transitions are involved: First, there are anomalies in c/a ratio and Raman spectra at low pressures (P = 1 - 2 GPa); and second, the c/a ratio reaches unity at ca. P = 10 GPa, where a monoclinic (Mc) but metrically cubic transition occurs from the ambient tetragonal P4 mm structure in pure PbTiO3; whereas the Raman lines (forbidden in the cubic phase) remain until ca. 17 GPa, where a monoclinic-cubic transition is known in lead titanate.

High Pressure Experimental Studies on CuO: Indication of Re-entrant Multiferroicity at Room Temperature.

We have carried out detailed experimental investigations on polycrystalline CuO using dielectric constant, dc resistance, Raman spectroscopy and X-ray diffraction measurements at high pressures. Observation of anomalous changes both in dielectric constant and dielectric loss in the pressure range 3.7-4.4 GPa and reversal of piezoelectric current with reversal of poling field direction indicate to a change in ferroelectric order in CuO at high pressures. A sudden jump in Raman integrated intensity of Ag mode at 3.4 GPa and observation of Curie-Weiss type behaviour in dielectric constant below 3.7 GPa lends credibility to above ferroelectric transition. A slope change in the linear behaviour of the Ag mode and a minimum in the FWHM of the same indicate indirectly to a change in magnetic ordering. Since all the previous studies show a strong spin-lattice interaction in CuO, observed change in ferroic behaviour at high pressures can be related to a reentrant multiferroic ordering in the range 3.4 to 4.4 GPa, much earlier than predicted by theoretical studies. We argue that enhancement of spin frustration due to anisotropic compression that leads to change in internal lattice strain brings the multiferroic ordering to room temperature at high pressures.

Raman scattering study of InAs nanowires under high pressure.

The pressure-dependent phonon modes of InAs nanowires have been investigated by Raman spectroscopy under high pressure up to ∼58 GPa. X-ray diffraction measurements show that InAs nanowires at 21 GPa exhibit a phase transition from a wurtzite to an orthorhombic crystal structure, with a corresponding drastic change in the first-order Raman spectra. In the low-pressure regime, a linear increase in phonon frequencies is observed, whereas splitting between longitudinal and transversal optical phonon modes decreases as a function of applied pressure. The calculated mode Grüneisen parameters and Born's transverse effective charge indicate that the wurtzite InAs nanowires exhibit a more covalent nature under compression.

Reappearance of ferroelectric soft modes in the paraelectric phase of Pb(1-x)Ca(x)TiO3 at high pressures: Raman and x-ray diffraction studies.

High pressure Raman spectroscopy and x-ray diffraction measurements have been carried out on Pb(1-x)Ca(x)TiO(3) (x = 0.10 and 0.30). Using high pressure Raman spectroscopic data, it is observed that the phonon instability responsible for the ferroelectric phase reappears in the paraelectric phase after a critical pressure. The observed critical pressures in the Ca(2+) doped PbTiO(3) system are much lower than the unique pressures suggested for PbTiO(3) based materials. A suitable explanation is given to explain this lowering of critical pressure. It is also shown that the ferroelectric phase which stabilizes in the paraelectric phase has a tetragonal symmetry with space group I4cm.

High pressure investigations of Na0.025WO3: x-ray diffraction and Raman spectroscopy studies.

High pressure x-ray diffraction and Raman spectroscopy studies have been carried out on non-stoichiometric sodium tungsten bronze, Na(0.025)WO(3). The high pressure investigations reveal a phase transition at about 2 GPa by a change of space group symmetry from P2(1)/n to P2(1)/c in the monoclinic cell followed by a second structural transformation to a triclinic lattice around 18 GPa. There are volume changes with these structural transformations, which are driven by rotation and significant distortion of WO(6) octahedra due to the displacement of tungsten and oxygen atoms from their mean positions in the unit cell.