An infrared spectroscopic study of the low-spin to intermediate-spin state ((1)A(1)-T-3(1)) transition in rare earth cobaltates, LnCoO(3) (Ln = La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO(3) (Ln = La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoo(3) and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition. (C) 2001 Published by Elsevier Science B.V.

Dielectric anomaly in strontium borate-bismuth vanadate glass nanocomposite

Transparent glass nanocomposites in the pseudo binary system (100 - x) SrB4O7 (SBO)-x Bi2VO5.5 (BiV) (0 less than or equal to n less than or equal to 70) were prepared by the splat quenching technique. The nano-crystallization of bismuth vanadate (BiV) in 50 SBO-50 BiV (in mol%) glass composite has been demonstrated. These were characterized for their structural, thermal and dielectric properties. As-quenched composites under study have been confirmed to be amorphous by X-ray powder diffraction (XRD) studies. The glass transition temperature (T-g) and crystallization temperatures (T-er) were determined using differential thermal analyses (DTA), High resolution transmission electron microscopic (HRTEM) studies carried out on heat-treated samples reveal the presence of spherical nanosize crystallites of Bi2VO5.5 (BiV) dispersed in the glassy matrix of SrB4O7 (SSO). The dielectric constant (epsilon (r)) and the dielectric loss (D) measurements were carried out on the as-quenched and heat-treated glass nanocomposite samples in the frequency range 100 Hz-10 MHz. The as-quenched and the heat-treated at two different temperatures (720 and 820 K) samples exhibited broad dielectric anomalies in the vicinity of the ferroelectric-to-paraelectric transition temperature of the parent BiV ceramics. The Curie-Weiss law was found to be valid at a temperature above the transition temperature, establishing the diffused nature of the transition. (C) 2001 Elsevier Science Ltd. All rights reserved.

On breaks of the Indian monsoon

For over a century, the term break has been used for spells in which the rainfall over the Indian monsoon zone is interrupted. The phenomenon of 'break monsoon' is of great interest because long intense breaks are often associated with poor monsoon seasons. Such breaks have distinct circulation characteristics (heat trough type circulation) and have a large impact on rainfed agriculture. Although interruption of the monsoon rainfall is considered to be the most important feature of the break monsoon, traditionally breaks have been identified on the basis of the surface pressure and wind patterns over the Indian region. We have defined breaks (and active spells) on the basis of rainfall over the monsoon zone. The rainfall criteria are chosen so as to ensure a large overlap with the traditional breaks documented by Ramamurthy (1969) and De et al (1998). We have identified these rainbreaks for 1901-89. We have also identified active spells on the basis of rainfall over the Indian monsoon zone. We have shown that the all-India summer monsoon rainfall is significantly negatively correlated with the number of rainbreak days (correlation coefficient -0.56) and significantly positively correlated with the number of active days (correlation coefficient 0.47). Thus the interannual variation of the all-India summer monsoon rainfall is shown to be related to the number of days of rainbreaks and active spells identified here. There have been several studies of breaks (and also active spells in several cases) identified on the basis of different criteria over regions differing in spatial scales (e.g., Webster et al 1998; Krishnan et al 2000; Goswami and Mohan 2000; and Annamalai and Slingo 2001). We find that there is considerable overlap between the rainbreaks we have identified and breaks based on the traditional definition. There is some overlap with the breaks identified by Krishnan et al (2000) but little overlap with breaks identified by Webster et al (1998). Further, there are three or four active-break cycles in a season according to Webster et al (1998) which implies a time scale of about 40 days for which Goswami and Mohan (2000), and Annamalai and Slingo'(2001) have studied breaks and active minus break fluctuations. On the other hand, neither the traditional breaks (Ramamurthy 1969; and De et al 1998) nor the rainbreaks occur every year. This suggests that the 'breaks' in these studies axe weak spells of the intraseasonal variation of the monsoon, which occur every year. We have derived the OLR and circulation patterns associated with rainbreaks and active spells and compared them with the patterns associated with breaks/active minus break spells from these studies. Inspite of differences in the patterns over the Indian region, there is one feature which is seen in the OLR anomaly patterns of breaks identified on the basis of different criteria as well as the rainbreaks identified in this paper viz., a quadrapole over the Asia-west Pacific region arising from anomalies opposite (same) in sign to those over the Indian region occurring over the equatorial Indian Ocean and northern tropical (equatorial) parts of the west Pacific. Thus it appears that this quadrapole is a basic feature of weak spells of the intraseasonal,variation over the Asia-west Pacific region. Since the rainbreaks are intense weak spells, this basic feature is also seen in the composite patterns of these breaks. We find that rainbreaks (active spells) are also associated with negative (positive) anomalies over a part of the cast Pacific suggesting that the convection over the Indian region is linked to that over the east Pacific not only on the interannual scale (as evinced by the link between the Indian summer monsoon rainfall and ENSO) but on the intraseasonal scale as well.

Low-temperature polaronic relaxations with variable range hopping conductivity in FeTiMO(6) (M = Ta,Nb,Sb)

Low-temperature dielectric measurements on FeTiMO(6) (M = Ta,Nb,Sb) rutile-type oxides at frequencies from 0.1 Hz to 10 MHz revealed anomalous dielectric relaxations with frequency dispersion. Unlike the high-temperature relaxor response of these materials, the low-temperature relaxations are polaronic in nature. The relationship between frequency and temperature of dielectric loss peak follows T(-1/4) behavior. The frequency dependence of ac conductivity shows the well-known universal dielectric response, while the dc conductivity follows Mott variable range hopping (VRH) behavior, confirming the polaronic origin of the observed dielectric relaxations. The frequency domain analysis of the dielectric spectra shows evidence for two relaxations, with the high-frequency relaxations following Mott VRH behavior more closely. Significantly, the Cr- and Ga-based analogs, CrTiNbO(6) and GaTiMO(6) (M = Ta,Nb), that were also studied, did not show these anomalies.

Unique Utilization of a Phosphoprotein Phosphatase Fold by a Mammalian Phosphodiesterase Associated with WAGR Syndrome

Metallophosphoesterase-domain-containing protein 2 (MPPED2) is a highly evolutionarily conserved protein with orthologs found from worms to humans. The human MPPED2 gene is found in a region of chromosome 11 that is deleted in patients with WAGR (Wilms tumor, aniridia, genitourinary anomalies, and mental retardation) syndrome, and MPPED2 may function as a tumor suppressor. However, the precise cellular roles of MPPED2 are unknown, and its low phosphodiesterase activity suggests that substrate hydrolysis may not be its prime function. We present here the structures of MPPED2 and two mutants, which show that the poor activity of MPPED2 is not only a consequence of the substitution of an active-site histidine residue by glycine but also due to binding of AMP or GMP to the active site. This feature, enhanced by structural elements of the protein, allows MPPED2 to utilize the conserved phosphoprotein-phosphatase-like fold in a unique manner, ensuring that its enzymatic activity can be combined with a possible role as a scaffolding or adaptor protein. (C) 2011 Elsevier Ltd. All rights reserved.

Dielectric response of BaZrO3/BaTiO3 and SrTiO3/BaZrO3 superlattices

Dielectric materials with high tunability, low loss, and desired range of permittivity are an attractive class of materials for a variety of applications in microwave components such as tunable filters, phase shifters, antennas, etc. In this article, we have investigated the low frequency dielectric properties of BaZrO3/BaTiO3 and SrTiO3/BaZrO3 superlattices of varying modulation periods for the potential application toward electrically tunable devices. The dielectric response of the superlattices as a function of temperature revealed remarkable stability for both types of superlattices, with no observed dielectric anomalies within that range. Dielectric losses were also nominally low with minimal variation within the measured temperature range. Sufficiently high tunability of ∼ 40% was observed for the BaZrO3/BaTiO3 superlattices at the lowest individual layer thicknesses. In comparison, the SrTiO3/BaZrO3 superlattices showed a minimum tunability for lowest period structures. It showed maximum tunability of ∼ 20% at 10 kHz and room temperature at an intermediate dimension of 3.85 nm periodicity superlattice. The tunability value degraded with increasing as well as decreasing periodicities for the SrTiO3/BaZrO3 superlattices. The dielectric response has been explained on the basis of size effects, interlayer coupling between dissimilar materials, domain contribution, and depolarizing electric fields.

Tuning of phonon anharmonicity in pyrochlore titanates: temperature-dependent Raman studies of Sm2Ti2-xZrxO7 (x=0, 1/2, 3/4, and 2)and stuffed spin-ice Ho2+xTi2-xO7-x/2 (x=0, 1/3, and 2/3)

Anomalous temperature dependence of Raman phonon wavenumbers attributed to phononphonon anharmonic interactions has been studied in two different families of pyrochlore titanates. We bring out the role of the ionic size of titanium and the inherent vacancies of pyrochlore in these anomalies by studying the effect of replacement of Ti4?+ by Zr4?+ in Sm2Ti2O7 and by stuffing Ho3?+ in place of Ti4?+ in Ho2Ti2O7 with appropriate oxygen stoichiometry. Our results show that an increase in the concentration of the larger ion, i.e. Zr4?+ or Ho3?+, reduces the phonon anomalies, thus implying a decrease in the phononphonon anharmonic interactions. In addition, we find signatures of coupling between a phonon and crystal field transition in Sm2Ti2O7, manifested as an unusual increase in the phonon intensity with increasing temperature. Copyright (c) 2011 John Wiley & Sons, Ltd.

Coupled phonons, magnetic excitations, and ferroelectricity in AlFeO3: Raman and first-principles studies

We determine the nature of coupled phonons and magnetic excitations in AlFeO3 using inelastic light scattering from 5 to 315 K covering a spectral range from 100 to 2200 cm(-1) and complementary first-principles density functional theory-based calculations. A strong spin-phonon coupling and magnetic ordering-induced phonon renormalization are evident in (1) anomalous temperature dependence of many modes with frequencies below 850 cm(-1), particularly near the magnetic transition temperature T-c approximate to 250 K, and (2) distinct changes in band positions of high-frequency Raman bands between 1100 and 1800 cm(-1); in particular, a broad mode near 1250 cm(-1) appears only below T-c, attributed to the two-magnon Raman scattering. We also observe weak anomalies in the mode frequencies similar to 100 K due to a magnetically driven ferroelectric phase transition. Understanding of these experimental observations has been possible on the basis of first-principles calculations of the phonons' spectrum and their coupling with spins.

Anomalous structural and dynamical phase transitions of soft colloidal binary mixtures

We report microscopic structural and dynamical measurements on binary mixtures of homopolymers and polymer grafted nanoparticles at high densities in good solvent. We find strong and unexpected anomalies in the structure and dynamics of these binary mixtures, including appearance of spontaneous orientational alignment, as a function of added homopolymers of different molecular weights. Our experiments point to the possibility of exploiting the phase space in density and homopolymer size, of such hybrid systems, to create new materials with novel structural and physical properties.

Signatures of Indian ocean Dipole and El Nino-Southern Oscillation events in sea level variations in the Bay of Bengal

We investigate the impact of the Indian Ocean Dipole (IOD) and El Nino and the Southern Oscillation (ENSO) on sea level variations in the North Indian Ocean during 1957-2008. Using tide-gauge and altimeter data, we show that IOD and ENSO leave characteristic signatures in the sea level anomalies (SLAs) in the Bay of Bengal. During a positive IOD event, negative SLAs are observed during April-December, with the SLAs decreasing continuously to a peak during September-November. During El Nino, negative SLAs are observed twice (April-December and November-July), with a relaxation between the two peaks. SLA signatures during negative IOD and La Nina events are much weaker. We use a linear, continuously stratified model of the Indian Ocean to simulate their sea level patterns of IOD and ENSO events. We then separate solutions into parts that correspond to specific processes: coastal alongshore winds, remote forcing from the equator via reflected Rossby waves, and direct forcing by interior winds within the bay. During pure IOD events, the SLAs are forced both from the equator and by direct wind forcing. During ENSO events, they are primarily equatorially forced, with only a minor contribution from direct wind forcing. Using a lead/lag covariance analysis between the Nino-3.4 SST index and Indian Ocean wind stress, we derive a composite wind field for a typical El Nino event: the resulting solution has two negative SLA peaks. The IOD and ENSO signatures are not evident off the west coast of India.

Molecular probe dynamics reveals suppression of ice-like regions in strongly confined supercooled water

The structure of the hydrogen bond network is a key element for understanding water's thermodynamic and kinetic anomalies. While ambient water is strongly believed to be a uniform, continuous hydrogen-bonded liquid, there is growing consensus that supercooled water is better described in terms of distinct domains with either a low-density ice-like structure or a high-density disordered one. We evidenced two distinct rotational mobilities of probe molecules in interstitial supercooled water of polycrystalline ice Banerjee D, et al. (2009) ESR evidence for 2 coexisting liquid phases in deeply supercooled bulk water. Proc Natl Acad Sci USA 106: 11448-11453]. Here we show that, by increasing the confinement of interstitial water, the mobility of probe molecules, surprisingly, increases. We argue that loose confinement allows the presence of ice-like regions in supercooled water, whereas a tighter confinement yields the suppression of this ordered fraction and leads to higher fluidity. Compelling evidence of the presence of ice-like regions is provided by the probe orientational entropy barrier which is set, through hydrogen bonding, by the configuration of the surrounding water molecules and yields a direct measure of the configurational entropy of the same. We find that, under loose confinement of supercooled water, the entropy barrier surmounted by the slower probe fraction exceeds that of equilibrium water by the melting entropy of ice, whereas no increase of the barrier is observed under stronger confinement. The lower limit of metastability of supercooled water is discussed.

c-theorems in arbitrary dimensions

The dilaton action in 3 + 1 dimensions plays a crucial role in the proof of the a-theorem. This action arises using Wess-Zumino consistency conditions and crucially relies on the existence of the trace anomaly. Since there are no anomalies in odd dimensions, it is interesting to ask how such an action could arise otherwise. Motivated by this we use the AdS/CFT correspondence to examine both even and odd dimensional conformal field theories. We find that in even dimensions, by promoting the cutoff to a field, one can get an action for this field which coincides with the Wess-Zumino action in flat space. In three dimensions, we observe that by finding an exact Hamilton-Jacobi counterterm, one can find a non-polynomial action which is invariant under global Weyl rescalings. We comment on how this finding is tied up with the F-theorem conjectures.

Subdiffusion in hair bundle dynamics: The role of protein conformational fluctuations

The detection of sound signals in vertebrates involves a complex network of different mechano-sensory elements in the inner ear. An especially important element in this network is the hair bundle, an antenna-like array of stereocilia containing gated ion channels that operate under the control of one or more adaptation motors. Deflections of the hair bundle by sound vibrations or thermal fluctuations transiently open the ion channels, allowing the flow of ions through them, and producing an electrical signal in the process, eventually causing the sensation of hearing. Recent high frequency (0.1-10 kHz) measurements by Kozlov et al. Proc. Natl. Acad. Sci. U. S. A. 109, 2896 (2012)] of the power spectrum and the mean square displacement of the thermal fluctuations of the hair bundle suggest that in this regime the dynamics of the hair bundle are subdiffusive. This finding has been explained in terms of the simple Brownian motion of a filament connecting neighboring stereocilia (the tip link), which is modeled as a viscoelastic spring. In the present paper, the diffusive anomalies of the hair bundle are ascribed to tip link fluctuations that evolve by fractional Brownian motion, which originates in fractional Gaussian noise and is characterized by a power law memory. The predictions of this model for the power spectrum of the hair bundle and its mean square displacement are consistent with the experimental data and the known properties of the tip link. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4768902]

All flavours of El Nino have similar early subsurface origins

The El Nino/Southern Oscillation phenomenon, characterized by anomalous sea surface temperatures and winds in the tropical Pacific, affects climate across the globe(1). El Ninos occur every 2-7 years, whereas the El Nino/Southern Oscillation itself varies on decadal timescales in frequency and amplitude, with a different spatial pattern of surface anomalies(2) each time the tropical Pacific undergoes a regime shift. Recent work has shown that Bjerknes feedback(3,4) (coupling of the atmosphere and the ocean through changes in equatorial winds driven by changes in sea surface temperature owing to suppression of equatorial upwelling in the east Pacific) is not necessary(5) for the development of an El Nino. Thus it is unclear what remains constant through regimes and is crucial for producing the anomalies recognized as El Nino. Here we show that the subsurface process of discharging warm waters always begins in the boreal summer/autumn of the year before the event (up to 18 months before the peak) independent of regimes, identifying the discharge process as fundamental to the El Nino onset. It is therefore imperative that models capture this process accurately to further our theoretical understanding, improve forecasts and predict how the El Nino/Southern Oscillation may respond to climate change.

A study of vertical cloud structure of the Indian summer monsoon using CloudSat data

Precise specification of the vertical distribution of cloud optical properties is important to reduce the uncertainty in quantifying the radiative impacts of clouds. The new global observations of vertical profiles of clouds from the CloudSat mission provide opportunities to describe cloud structures and to improve parameterization of clouds in the weather and climate prediction models. In this study, four years (2007-2010) of observations of vertical structure of clouds from the CloudSat cloud profiling radar have been used to document the mean vertical structure of clouds associated with the Indian summer monsoon (ISM) and its intra-seasonal variability. Active and break monsoon spells associated with the intra-seasonal variability of ISM have been identified by an objective criterion. For the present analysis, we considered CloudSat derived column integrated cloud liquid and ice water, and vertically profiles of cloud liquid and ice water content. Over the South Asian monsoon region, deep convective clouds with large vertical extent (up to 14 km) and large values of cloud water and ice content are observed over the north Bay of Bengal. Deep clouds with large ice water content are also observed over north Arabian Sea and adjoining northwest India, along the west coast of India and the south equatorial Indian Ocean. The active monsoon spells are characterized by enhanced deep convection over the Bay of Bengal, west coast of India and northeast Arabian Sea and suppressed convection over the equatorial Indian Ocean. Over the Bay of Bengal, cloud liquid water content and ice water content is enhanced by similar to 90 and similar to 200 % respectively during the active spells. An interesting feature associated with the active spell is the vertical tilting structure of positive CLWC and CIWC anomalies over the Arabian Sea and the Bay of Bengal, which suggests a pre-conditioning process for the northward propagation of the boreal summer intra-seasonal variability. It is also observed that during the break spells, clouds are not completely suppressed over central India. Instead, clouds with smaller vertical extent (3-5 km) are observed due to the presence of a heat low type of circulation. The present results will be useful for validating the vertical structure of clouds in weather and climate prediction models.