Investigation of the vibrational modes of ZnO grown by MOCVD on different orientation planes

Wurtzite ZnO thin films were prepared on sapphire substrate by metal organic chemical vapor deposition (MOCVD). Raman scattering studies on different crystallographic textures were performed in the backscattering geometry, and polarization effect is investigated in different configurations and . ZnO Raman modes are investigated in each texture. In the case of ZnO thin film deposed on r‐() sapphire plane and using backscattering geometry, new Raman line was observed at 390 cm⁻¹ because this mode has not been noticed in this geometry. It is shown that the frequencies of the quasi‐phonon modes of the examined thin film are in good agreement with the theoretical values calculated within the framework of Loudon model. Copyright © 2014 John Wiley & Sons, Ltd.     

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 and nonmagnetic 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 F_2g 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 T_C ~ 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 dT_C/dP = + 5.9 K/GPa. Temperature dependence of other phonons has also been studied at various pressures up 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 © 2012 John Wiley & Sons, Ltd.     

DFT‐assisted interpretation of the Raman spectra of hydrogen‐ordered ice XV

The vibrational spectra of the condensed phases of water often show broad and strongly overlapping spectral features which can make spectroscopic interpretations and peak assignments difficult. The Raman spectra of hydrogen‐ordered H₂O and D₂O ice XV are reported here, and it is shown that the spectra can be fully interpreted in terms of assigning normal modes to the various spectral features by using density functional theory (DFT) calculations. The calculated lattice‐vibration spectrum of the experimental antiferroelectric structure is in good agreement with the experimental data whereas the spectrum of a ferroelectric Cc structure, which computational studies have suggested as the crystal structure of ice XV, differs substantially. Moreover, the calculated coupled O–H stretch spectrum also seems in better agreement with the experiment than the calculated spectrum for the Cc structure. Both the hydrogen bonds as well as the covalent bonds appear to be stronger in hydrogen‐ordered ice XV than in the hydrogen‐disordered counterpart ice VI. A new type of stretching mode is identified, and it is speculated that this kind of mode might be relevant for other condensed water phases as well. Furthermore, the ice XV spectra are compared to the spectra of ice VIII which is the only other high‐pressure phase of ice for which detailed spectroscopic assignments have been made so far. In summary, we have established a link between crystallographic data and spectroscopic information in the case of ice XV by using DFT‐calculated spectra. Such correlations may eventually help interpreting the vibrational spectra of more structurally‐disordered aqueous systems. Copyright © 2012 John Wiley & Sons, Ltd.     

Raman spectroscopy of M3B7O13X boracites (M = Cr,Co,Ni,Cu,Zn,Cd; X = Cl,Br,I)

We report results of a Raman study on single crystals of 16 boracites M₃B₇O₁₃X (M = Cr,Co,Ni,Cu,Zn,Cd; X = Cl,Br,I) over a broad temperature range. The Raman modes for all boracites in their high‐temperature prototype cubic (F3c) phase are compared. With decreasing temperature, most (but not all) compounds present a transition to the low‐temperature orthorhombic phase (Pca2₁) or to a sequence of orthorhombic, monoclinic (Pa), and trigonal (R3c) phases. The variations of the Raman spectra through different phases are studied in detail. Special attention is paid to the temperature hysteresis near the transitions and the dependence of transition temperature on the direction of crystal growth for the same material. Copyright © 2014 John Wiley & Sons, Ltd.     

Hyper‐Raman and Raman scattering in paratellurite TeO2

Raman spectra of the tetragonal structure of paratellurite TeO₂ have been revisited avoiding anomalous polarization‐selection‐rules violations previously observed and due to optical activity. We present a complementary hyper‐Raman scattering study of paratellurite. Wavenumber and symmetry assignments are given for all expected 21 Raman active optical branches, except one LO component (out of the eight expected TO–LO pairs) of the polar doublet E modes. Also, the four expected hyper‐Raman active A₂ (TO) modes have been observed. Moreover, we have observed a strong Kleinman‐disallowed hyper‐Rayleigh signal, which is tentatively assigned as a first evidence of hyper‐Rayleigh optical activity. Copyright © 2013 John Wiley & Sons, Ltd.     

Half‐Maximal Supersymmetry from Exceptional Field Theory

We study ‐dimensional half‐maximal flux backgrounds using exceptional field theory. We define the relevant generalised structures and also find the integrability conditions which give warped half‐maximal Minkowski_D and AdS_D vacua. We then show how to obtain consistent truncations of type II / 11‐dimensional SUGRA which break half the supersymmetry. Such truncations can be defined on backgrounds admitting exceptional generalised structures, where , and N is the number of vector multiplets obtained in the lower‐dimensional theory. Our procedure yields the most general embedding tensors satisfying the linear constraint of half‐maximal gauged SUGRA. We use this to prove that all half‐maximal warped AdS_D and Minkowski_D vacua of type II / 11‐dimensional SUGRA admit a consistent truncation keeping only the gravitational supermultiplet. We also show to obtain heterotic double field theory from exceptional field theory and comment on the M‐theory / heterotic duality. In five dimensions, we find a new SO(5, N ) double field theory with a ‐dimensional extended space. Its section condition has one solution corresponding to 10‐dimensional supergravity and another yielding six‐dimensional SUGRA.     

Vibrational and reorientational dynamics,crystal structure and solid–solid phase transition studies in [Ca(H2O)6]Cl2 supported by theoretical (DFT) calculations

[Ca(H₂O)₆]Cl₂ between 93 and 300 K possesses two solid phases. One phase transition (PT) of the first‐order type at = 218.0 K (on heating) and = 208.0 K (on cooling) was determined by differential scanning calorimetry. Thermal hysteresis of this PT (10 K), as well as the heat flow anomaly sharpness, suggests that the detected PT is a first‐order one. The entropy change value [ΔS ≈ 8.5 J mol⁻¹ K⁻¹ ≈ Rln(2.8)] associated with the observed PT suggests a moderate degree of molecular dynamical disorder of the high‐temperature phase. The temperature dependencies of the full width at half maximum values of the infrared band are due to ρ(H₂O)A₂ mode (at 205 cm⁻¹), and two Raman bands are arising from τ(H₂O)E and τ(H₂O)A₁ modes (at ca. 410 and 682 cm⁻¹, respectively), suggesting that the observed PT is associated with a sudden change of speed of the H₂O reorientational motions. The estimated mean value of activation energy for the reorientation of the H₂O ligands in the high‐temperature phase is ca. 11.4 kJ mol⁻¹ from Raman spectroscopy and 11.9 kJ mol⁻¹ from infrared spectroscopy. X‐ray single‐crystal diffraction measurement and spectroscopic studies (infrared, Raman and inelastic neutron scattering) also confirm that [Ca(H₂O)₆]Cl₂ includes two sets of differently bonded H₂O molecules. Ab initio calculations of the complete unit cell of one molecule of calcium chloride with a different number of water molecules (2, 4 and 6) have also been carried out. A comparison of Fourier Transform Infrared (FT‐IR), Fourier Transform Raman Scattering (FT‐RS) and inelastic neutron scattering spectroscopies results with periodic density functional theory calculations was used to provide a complete assignment of the vibrational spectra of [Ca(H₂O)₆]Cl₂. Copyright © 2016 John Wiley & Sons, Ltd.     

A comparison between ab initio calculated and measured Raman spectrum of triclinic albite (NaAlSi3O8)

Albite is one of the most common minerals in the Earth's crust, and its polymorphs can be found in rocks with different cooling histories. The characteristic spectrum of vibration of the albite mineral reflects its structural Si/Al ordering. In this study, we report on the comparison between the Raman spectra measured on a natural and fully ordered (as deduced on the basis of single‐crystal X‐ray diffraction data) ‘low albite’, NaAlSi₃O₈, and those calculated at the hybrid Hartree–Fock/density functional theory level by employing the WC1LYP Hamiltonian, which has proven to give excellent agreement between calculated and experimentally measured vibrational wavenumbers in silicate minerals. All the 39 expected A_g modes are identified in the Raman spectra, and their wavenumbers and intensities, in different scattering configurations, correspond well to the calculated ones. The average absolute discrepancy is ~3.4 cm⁻¹, being the maximum discrepancy |Δv|_max ~ 10.3 cm⁻¹. The very good quality of the WC1LYP results allows for reliable assignments of the Raman features to specific patterns of atomic vibrational motion. Copyright © 2015 John Wiley & Sons, Ltd.     

Nodal theorems for the Dirac equation in d ≥ 1 dimensions

A single particle obeys the Dirac equation in spatial dimensions and is bound by an attractive central monotone potential that vanishes at infinity. In one dimension, the potential is even, and monotone for The asymptotic behavior of the wave functions near the origin and at infinity are discussed. Nodal theorems are proven for the cases and , which specify the relationship between the numbers of nodes n₁ and n₂ in the upper and lower components of the Dirac spinor. For , whereas for if and if where and This work generalizes the classic results of Rose and Newton in 1951 for the case Specific examples are presented with graphs, including Dirac spinor orbits      

The Spin‐Charge‐Family Theory Offers Understanding of the Triangle Anomalies Cancellation in the Standard Model

The standard model has for massless quarks and leptons “miraculously” no triangle anomalies due to the fact that the sum of all possible traces — where and are the generators of one, of two or of three of the groups and U (1) — over the representations of one family of the left handed fermions and anti‐fermions (and separately of the right handed fermions and anti‐fermions), contributing to the triangle currents, is equal to zero. 1 - 4 It is demonstrated in this paper that this cancellation of the standard model triangle anomaly follows straightforwardly if the and are the subgroups of the orthogonal group , as it is in the spin‐charge‐family theory. 5 - 22 We comment on the anomaly cancellation, which works if handedness and charges are related “by hand”.     

Real‐time Raman spectroscopy measurements to study the uniaxial tension of isotactic polypropylene: a global overview of microstructural deformation mechanisms

Micro‐Raman spectroscopy was used to investigate the main deformation micromechanisms of isotactic polypropylene uniaxially stretched at constant temperature (T = 30 °C) under a constant true strain rate ( = 5.10⁻³ s⁻¹). To accurate measurements namely to be free of the recovering phenomenon which causes in most of the cases interference during post‐mortem analysis, we introduced a new experimental setup combining a Raman spectrometer with a tensile machine piloted by the VidéoTraction™ system. Microstructure is described by essential parameters such as the crystallinity index, the macromolecular orientation both in the crystalline and the amorphous phase, and distribution of the internal stress at the chemical bonds scale. For each, a well‐tried Raman spectral criterion was used. Cross‐checking of these results, obtained with a minimum of tensile tests, allows a more complete understanding of the deformation micromechanisms of semi‐crystalline polymer. Copyright © 2013 John Wiley & Sons, Ltd.     

Higher‐Dimensional Unification with continuous and fuzzy coset spaces as extra dimensions

We first review the Coset Space Dimensional Reduction (CSDR) programme and present the best model constructed so far based on the , 10‐dimensional E₈ gauge theory reduced over the nearly‐Kähler manifold with the additional use of the Wilson flux mechanism. Then we present the corresponding programme in the case that the extra dimensions are considered to be fuzzy coset spaces and the best model that has been constructed in this framework too. In both cases the best model appears to be the trinification GUT .     

Hodge numbers for CICYs with symmetries of order divisible by 4

We compute the Hodge numbers for the quotients of complete intersection Calabi‐Yau three‐folds by groups of orders divisible by 4. We make use of the polynomial deformation method and the counting of invariant Kähler classes. The quotients studied here have been obtained in the automated classification of V. Braun. Although the computer search found the freely acting groups, the Hodge numbers of the quotients were not calculated. The freely acting groups, G, that arise in the classification are either or contain , , or as a subgroup. The Hodge numbers for the quotients for which the group G contains or have been computed previously. This paper deals with the remaining cases, for which or . We also compute the Hodge numbers for 99 of the 166 CICY's which have quotients.     

Towards the Standard Model in F‐theory

This article explores possible embeddings of the Standard Model gauge group and its matter representations into F‐theory. To this end we construct elliptic fibrations with gauge group as suitable restrictions of a ‐fibration with rank‐two Mordell‐Weil group. We analyse the five inequivalent toric enhancements to gauge group along two independent divisors W₃ and W₂ in the base. For each of the resulting smooth fibrations, the representation spectrum generically consists of a bifundamental , three types of representations and five types of representations (plus conjugates), in addition to charged singlet states. The precise spectrum of zero‐modes in these representations depends on the 3‐form background. We analyse the geometrically realised Yukawa couplings among all these states and find complete agreement with field theoretic expectations based on their U(1) charges. We classify possible identifications of the found representations with the Standard Model field content extended by right‐handed neutrinos and extra singlets. The linear combination of the two abelian gauge group factors orthogonal to hypercharge acts as a selection rule which, depending on the specific model, can forbid dangerous dimension‐four and ‐five proton decay operators.     

Non‐Thermal Corrections to Hawking Radiation Versus the Information Paradox**

We provide a model‐independent argument indicating that for a black hole of entropy N the non‐thermal deviations from Hawking radiation, per each emission time, are of order , as opposed to . This fact abolishes the standard a priory basis for the information paradox.     

Raman light scattering,infrared absorption and DSC studies of the phase transition and vibrational and reorientational dynamics of H2O ligands and ClO4– anions in [Ba(H2O)3](ClO4)2

[Ba(H₂O)₃](ClO₄)₂ between 90 and 300 K possesses two solid phases. One phase transition of the first‐order type at: = 211.3 K (on heating) and = 204.6 K (on cooling) was determined by differential scanning calorimetry. The entropy change value (ΔS ≈ 15 Jmol^–1 K^–1), associated with the observed phase transition, indicates a moderate degree of molecular dynamical disorder. Both, vibrational and reorientational motions of H₂O ligands and ClO₄^– anions, in the high‐temperature and low‐temperature phases, were investigated by Fourier transform far‐infrared and middle‐infrared and Raman light scattering spectroscopies. The temperature dependences of the full‐width at half‐maximum values of the bands associated with ρ_w(H₂O) mode, in both infrared (~570 cm^–1) and Raman light scattering (~535 cm^–1) spectra, suggest that the observed phase transition is not associated with a sudden change of a speed of the H₂O reorientational motions. Ligands reorient fast, with correlation time of the order of several picoseconds, with a mean activation energy value E_a = 5.1 kJ mol^–1 in both high and low temperature phases. On the other hand, measurements of temperature dependences of full‐width at half‐maximum values of the infrared band at ~460 cm^–1, associated with δ_d(OClO)E mode, and Raman band at ~1105 cm^–1, associated with ν_as(ClO)F₂ mode, revealed the existence of a fast ClO₄^– reorientation in phase I and in phase II, with the E_a(I) and E_a(II) values equal to 8.0 and 6.5 kJ mol^–1, respectively. These reorientational motions of ClO₄^– are slightly distorted at the T_C. Fourier transform far‐infrared and middle‐infrared spectra with decreasing of temperature indicated characteristic changes at the vicinity of PT at T_C, which suggested lowering of the crystal structure symmetry. All these experimental facts suggest that the discovered phase transition is associated with small change of H₂O ligands and somewhat major change of ClO₄^– anions reorientational dynamics, and with insignificant change of the crystal structure, too. Copyright © 2012 John Wiley & Sons, Ltd.     

Theory of the Robin quantum wall in a linear potential. II. Thermodynamic properties

A theoretical analysis of the thermodynamic properties of the Robin wall characterized by the extrapolation length Λ in the electric field that pushes the particle to the surface is presented both in the canonical and two grand canonical representations and in the whole range of the Robin distance with the emphasis on its negative values which for the voltage‐free configuration support negative‐energy bound state. For the canonical ensemble, the heat capacity at exhibits a nonmonotonic behavior as a function of the temperature T with its pronounced maximum unrestrictedly increasing for the decreasing fields as and its location being proportional to . For the Fermi‐Dirac distribution, the specific heat per particle is a nonmonotonic function of the temperature too with the conspicuous extremum being preceded on the T axis by the plateau whose magnitude at the vanishing is defined as , with N being a number of the particles. The maximum of is the largest for and, similar to the canonical ensemble, grows to infinity as the field goes to zero. For the Bose‐Einstein ensemble, a formation of the sharp asymmetric feature on the ‐T dependence with the increase of N is shown to be more prominent at the lower voltages. This cusp‐like dependence of the heat capacity on the temperature, which for the infinite number of bosons transforms into the discontinuity of , is an indication of the phase transition to the condensate state. Some other physical characteristics such as the critical temperature and ground‐level population of the Bose‐Einstein condensate are calculated and analyzed as a function of the field and extrapolation length. Qualitative and quantitative explanation of these physical phenomena is based on the variation of the energy spectrum by the electric field.     

Relic photon temperature versus redshift and the cosmic neutrino background

Presuming that CMB photons are described by the deconfining phase of an SU(2) Yang‐Mills theory with the critical temperature for the deconfining‐preconfining phase transition matching the present CMB temperature K (SU(2)_CMB), we investigate how CMB temperature T connects with the cosmological scale factor a in a Friedmann‐Lemaître‐Robertson‐Walker Universe. Owing to a violation of conformal scaling at late times, the tension between the (instantaneous) redshift of reionisation from CMB observation () and quasar spectra () is repealed. Also, we find that the redshift of CMB decoupling moves from to which questions ΛCDM cosmology at high redshifts. Adapting this model to the conventional physics of three flavours of massless cosmic neutrinos, we demonstrate inconsistency with the value N_eff ～ 3.36 extracted from Planck data. Interactions between cosmic neutrinos and the CMB implies a common temperature T of (no longer separately conserved) CMB and neutrino fluids. N_eff ～ 3.36 then entails a universal, temperature induced cosmic neutrino mass with . Our above results on z_re and z_dec, derived from SU(2)_CMB alone, are essentially unaffected when including such a neutrino sector.

     

Raman spectroscopy of ionic liquids derived from 1‐n‐butyl‐3‐methylimidazolium chloride and niobium chloride or zinc chloride mixtures

Anionic species formed in mixtures of 1‐n‐butyl‐3‐methylimidazolium chloride (BMICl) with different amounts of niobium pentachloride (NbCl₅) or zinc dichloride (ZnCl₂) were investigated by Raman spectroscopy. In the BMICl and NbCl₅ ionic mixtures the presence of the anion NbCl₆⁻ was detected for all compositions (molar fraction, X) and a mixture of this anion and the neutral Nb₂Cl₁₀ in acid ones. Two different anions were observed for basic mixtures of BMICl and ZnCl₂: ZnCl₄²⁻(0 < X < 0.35) and Zn₂Cl₆²⁻(X > 0.3), whereas for acidic ones three species were detected: Zn₂Cl₆²⁻(X < 0.7), Zn₃Cl₈²⁻(X > 0.7) and Zn₄Cl₁₀²⁻(X > 0.7). It has also been observed that in both cases, the formation of larger anions causes a shift of the C H stretching modes to higher wavenumbers as the result of a decrease in the hydrogen bond between Cl and the hydrogens from the cation. Copyright © 2008 John Wiley & Sons, Ltd.