Dynamics of zeolite cage and its effect on the diffusion properties of sorbate: persistence of diffusion anomaly in NaA zeolite

Recent computer simulations on zeolites Y and A have found that the diffusion coefficient and the rate of intercage diffusion exhibit, apart from a linear dependence on the reciprocal of the square of the sorbate diameter, an anomalous peak as sorbate diameter approaches the window diameter. Here we report molecular dynamics simulations of zeolite NaA incorporating framework flexibility as a function of sorbate diameter in order to verify the existence of anomalous diffusion. Results suggest persistence of anomalous diffusion or ring effect. This suggests that the anomalous behavior is a general effect characteristic of zeolites Y and A. The barrier for diffusion across the eight-ring window is seen to be negative and is found to decrease with sorbate size. The effect of sorbate on the cage motion has also been investigated. Results suggest that the window expands during intercage migration only if the sorbate size is comparable to the window diameter. Flexible cage simulations yield a higher value for the diffusion coefficient and also the rate of intercage diffusion. This increase has been shown to be due to an increase in the intercage diffusions via the centralized diffusion mode rather than the surface-mediated mode. It is shown that this increase arises from an increase in the single particle density distribution in the region near the cage center.

Investigation on the Magnetic Anomaly and the Role of Orbital Moment on the Magnetic Properties of LaMn0.5Co0.5O3

Two distinct ferromagnetic phases are present in LaMn0.5Co0.5O3 for which the spin-only magnetic moment calculated from the high temperature dc susceptibility is found to be unusually high. Such a high moment can only be accounted for by assigning the valence state of the cations to Mn2+-Co4+. This is unrealistic as the earlier report based on X-ray absorption spectroscopy (XAS) has suggested the valence state to be mainly Mn4+-Co2+ with traces of Co3+. Also from our studies using XAS, it is found that the valence state is mainly Mn4+-Co2+. In addition, no notable difference is observed in the minor Co3+ present in both phases. Our results based on X-ray magnetic circular dichroism studies (XMCD) reveal the presence of ``distinct'' high orbital moment associated with Co2+ for both phases. Thus it is found that the distinctness of the orbital moment also plays a vital role in determining the magnetic moment and T-c of both phases of LaMn0.5Co0.5O3. By considering the orbital moment obtained from XMCD, the anomaly in the paramagnetic susceptibility is resolved and thus we are able to assign the valence state to Mn4+-Co2+ configuration. The difference in the magnitude of orbital moment in both phases is believed to be due to the crystal field effects.

Diffusion Anomaly in Silicalite and VPI-5 from Molecular Dynamics Simulations

Molecular dynamics (MD) simulations on rigid and flexible framework models of silicalite and a rigid framework model of the aluminophosphate VPI-5 for different sorbate diameters are reported. The sorbate-host interactions are modeled in terms of simple atom-atom Lennard-Jones interactions. The results suggest that the diffusion coefficient exhibits an anomaly as gamma approaches unity. The MD results confirm the existence of a linear regime for sorbate diameters significantly smaller than the channel diameter and an anomalous regime observed for sorbate diameters comparable to the channel diameter. The power spectra obtained by Fourier transformation of the velocity autocorrelation function indicate that there is an increase in the intensity of the low-frequency component for the velocity component parallel to the direction of motion for the sorbate diameter in the anomalous regime. The present results suggest that the diffusion anomaly is observed irrespective of (1) the geometry and topology of the pore structure and (2) the nature of the host material. The results are compared with the work of Derouane and co-workers, who have suggested the existence of ''floating molecules'' on the basis of earlier theoretical and computational approaches.

Phonon interference in BaTiO3: High-pressure Raman study

Raman experiments have been carried out on single crystals of BaTiO3 as a function of pressure up to 3.5 GPa across the ferroelectric (tetragonal) to paraelectric (cubic) phase transition. The unusual features in the Raman spectra associated with the interference effects due to coupling of the three A1(TO) phonons are studied quantitatively to obtain the pressure dependence of the line shape parameters and the coupling constants. The frequencies of the middle and highest-frequency modes as well as the linewidth of the middle mode show interesting pressure dependence.

Raman evidence for the superconducting gap and spin-phonon coupling in the superconductor Ca( Fe0.95Co0.05)(2)As-2

Inelastic light scattering studies on a single crystal of electron-doped Ca(Fe0.95Co0.05)(2)As-2 superconductor, covering the tetragonal-to-orthorhombic structural transition as well as the magnetic transition at T-SM similar to 140 K and the superconducting transition temperature T-c similar to 23 K, reveal evidence for superconductivity-induced phonon renormalization. In particular, the phonon mode near 260 cm(-1) shows hardening below T-c, signaling its coupling with the superconducting gap. All three Raman active phonon modes show anomalous temperature dependence between room temperature and T-c, i.e. the phonon frequency decreases with lowering temperature. Further, the frequency of one of the modes shows a sudden change in temperature dependence at TSM. Using first-principles density functional theory based calculations, we show that the low temperature phase (T-c < T < T-SM) exhibits short-ranged stripe antiferromagnetic ordering, and estimate the spin-phonon couplings that are responsible for these phonon anomalies.

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.

Multi-Mode Phonon-Controlled Field Emission from Carbon Nanotubes: Modeling and Experiments

The main idea proposed in this paper is that in a vertically aligned array of short carbon nanotubes (CNTs) grown on a metal substrate, we consider a frequency dependent electric field, so that the mode-specific propagation of phonons, in correspondence with the strained band structure and the dispersion curves, take place. We perform theoretical calculations to validate this idea with a view of optimizing the field emission behavior of the CNT array. This is the first approach of its kind, and is in contrast to the the conventional approach where a DC bias voltage is applied in order to observe field emission. A first set of experimental results presented in this paper gives a clear indication that phonon-assisted control of field emission current in CNT based thin film diode is possible.

Influence of two photon absorption induced free carriers on coherent polariton and phonon generation in ZnTe crystals

Combination of femtosecond Kerr, two photon absorption, and impulsive stimulated Raman scattering (ISRS) experiments have been carried out to investigate the effect of pulse energy and crystal temperature on the generation of coherent polaritons and phonons in 〈110〉 cut ZnTe single crystals of three different resistivities. We demonstrate that the effect of two photon induced free carriers on the creation of both the polaritons and phonons is largest at 4 K where the free carrier lifetime is enhanced. The temperature dependant ISRS on high and low purity ZnTe crystals allows us to unambiguously assign the phonon mode at 3.5 THz to the longitudinal acoustic mode at X-point in the Brillouin zone, LA(X).

Spin-Electron-Phonon Excitation in Re-based Half-Metallic Double Perovskites

A remarkable hardening (similar to 30 cm(-1)) of the normal mode of vibration associated with the symmetric stretching of the oxygen octahedra for the Ba2FeReO6 and Sr2CrReO6 double perovskites is observed below the corresponding magnetic ordering temperatures. The very large magnitude of this effect and its absence for the antisymmetric stretching mode provide evidence against a conventional spin-phonon coupling mechanism. Our observations are consistent with a collective excitation formed by the combination of the vibrational mode with oscillations of Fe or Cr 3d and Re 5d occupations and spin magnitudes.

Symmetry-dependent phonon renormalization in monolayer MoS2 transistor

A strong electron-phonon interaction which limits the electronic mobility of semiconductors can also have significant effects on phonon frequencies. The latter is the key to the use of Raman spectroscopy for nondestructive characterization of doping in graphene-based devices. Using in situ Raman scattering from a single-layer MoS2 electrochemically top-gated field-effect transistor (FET), we show softening and broadening of the A(1g) phonon with electron doping, whereas the other Raman-active E-2g(1) mode remains essentially inert. Confirming these results with first-principles density functional theory based calculations, we use group theoretical arguments to explain why the A(1g) mode specifically exhibits a strong sensitivity to electron doping. Our work opens up the use of Raman spectroscopy in probing the level of doping in single-layer MoS2-based FETs, which have a high on-off ratio and are of technological significance.

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.

Superconducting fluctuations and anomalous phonon renormalization much above superconducting transition temperature in Ca4Al2O5.7Fe2As2

Raman studies on Ca4Al2O5.7Fe2As2 superconductor in the temperature range of 5K to 300 K, covering the superconducting transition temperature T-c = 28.3 K, reveal that the Raman mode at similar to 230 cm(-1) shows a sharp jump in frequency by similar to 2% and linewidth increases by similar to 175% at T-o similar to 60 K. Below T-o, anomalous softening of the mode frequency and a large decrease by similar to 10 cm(-1) in the linewidth are observed. These precursor effects at T-0 (similar to 2T(c)) are attributed to significant superconducting fluctuations, possibly enhanced due to reduced dimensionality arising from weak coupling between the well separated (similar to 15 angstrom) Fe-As layers in the unit cell. A large blue-shift of the mode frequency between 300 K and 60 K (similar to 7%) indicates strong spin-phonon coupling in this superconductor. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4724206]

Phonon anomalies and structural transition in spin ice Dy2Ti2O7: a simultaneous pressure-dependent and temperature-dependent Raman study

We revisit the assignment of Raman phonons of rare-earth titanates by performing Raman measurements on single crystals of O18 isotope-rich spin ice Dy2Ti2O718 and nonmagnetic Lu2Ti2O718 pyrochlores and compare the results with their O16 counterparts. We show that the low-wavenumber Raman modes below 250 cm-1 are not due to oxygen vibrations. A mode near 200 cm-1, commonly assigned as F2g phonon, which shows highly anomalous temperature dependence, is now assigned to a disorder-induced Raman active mode involving Ti4+ vibrations. Moreover, we address here the origin of the new Raman mode, observed below TC similar to 110 K in Dy2Ti2O7, through a simultaneous pressure-dependent and temperature-dependent Raman study. Our study confirms the new mode to be a phonon mode. We find that dTC/dP = + 5.9 K/GPa. Temperature dependence of other phonons has also been studied at various pressures up to similar to 8 GPa. We find that pressure suppresses the anomalous temperature dependence. The role of the inherent vacant sites present in the pyrochlore structure in the anomalous temperature dependence is also discussed. Copyright (c) 2012 John Wiley & Sons, Ltd.

Acoustic and optical phonon dynamics from femtosecond time-resolved optical spectroscopy of the superconducting iron pnictide Ca(Fe0.944Co0.056)(2)As-2

We report the temperature evolution of coherently excited acoustic and optical phonon dynamics in the superconducting iron pnictide single crystal Ca(Fe0.944Co0.056)(2)As-2 across the spin density wave transition at T-SDW similar to 85 K and the superconducting transition at T-SC similar to 20 K. The strain pulse propagation model applied to the generation of the acoustic phonons yields the temperature dependence of the optical constants, and longitudinal and transverse sound velocities in the temperature range from 3.1 K to 300 K. The frequency and dephasing times of the phonons show anomalous temperature dependence below T-SC indicating a coupling of these low-energy excitations with the Cooper-pair quasiparticles. A maximum in the amplitude of the acoustic modes at T similar to 170 is seen, attributed to spin fluctuations and strong spin-lattice coupling before T-SDW. Copyright (c) EPLA, 2012

A physics-based flexural phonon-dependent thermal conductivity model for single layer graphene

In this paper, we address a physics-based closed-form analytical model of flexural phonon-dependent diffusive thermal conductivity (kappa) of suspended rectangular single layer graphene sheet. A quadratic dependence of the out-of-plane phonon frequency, generally called flexural phonons, on the phonon wave vector has been taken into account to analyze the behavior of kappa at lower temperatures. Such a dependence has further been used for the determination of second-order three-phonon Umklapp and isotopic scatterings. We find that these behaviors in our model are best explained through the upper limit of Debye cut-off frequency in the second-order three-phonon Umklapp scattering of the long phonon waves that actually remove the thermal conductivity singularity by contributing a constant scattering rate at low frequencies and note that the out-of-plane Gruneisen parameter for these modes need not be too high. Using this, we clearly demonstrate that. follows a T-1.5 and T-2 law at lower and higher temperatures in the absence of isotopes, respectively. However in their presence, the behavior of kappa sharply deviates from the T-2 law at higher temperatures. The present geometry-dependent model of kappa is found to possess an excellent match with various experimental data over a wide range of temperatures which can be put forward for efficient electro-thermal analyses of encased/supported graphene.