Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part I: Reanalysis of the 3680 Å and 4100 Å absorption systems of oxalyl chloride

The vapor-phase absorption spectrum of oxalyl chloride in the 3000-4180 Å region has been re-examined at high resolution. Singlet-singlet and singlet-triplet electronic transitions of the trans-conformer found in the spectrum are in agreement with earlier works [W.J. Balfour, G.W. King, J. Mol. Spectrosc. 26 (1968) 384-397; ibid. 27 (1968) 432-442]. Torsion levels of trans-oxalyl chloride in the ground and excited and states were found for the first time. Ab initio calculations of structures for conformers of oxalyl chloride in the ground and lowest excited electronic states explain the absence of second conformer transitions in the vibronic absorption spectrum.     

The effect of the Bi source on optical properties of Bi2Te3 nanostructures

nanostructures were synthesized by using different Bi sources via a simple solvothermal process, in which and BiCl₃ were used as the Bi sources. Optical properties of nanostructures prepared with and BiCl₃ as the Bi sources were investigated by micro-Raman spectroscopy. The Raman scattering spectrum of hexagonal nanoplates prepared by using as the Bi source shows that the infrared (IR) active mode A_1u, which must be odd parity and is Raman forbidden for bulk crystal due to its inversion symmetry, is greatly activated and shows up clearly in the Raman scattering spectrum. We attribute the appearance of the infrared active A_1u mode in the Raman spectrum to crystal symmetry breaking of hexagonal nanoplates. However, the Raman scattering spectrum of nanostructures with irregular shape prepared by using as the Bi source only exhibits the two characteristic Raman modes of crystals. Micro-Raman measurements on nanostructures with different morphologies offer us a potential way to tailor optical properties of nanostructures by controlling the morphologies of the nanostructures, which is very important for practical applications of nanostructures in thermoelectric devices.     

Model calculations of the energy band structures of double stranded DNA in the presence of water and Na ions

Using the ab initio Hartree-Fock crystal orbital method in its linear combination of atomic orbitals form we have calculated the band structures of poly(-) and poly(-). Here, besides the nucleotide bases, the sugar and phosphate parts of the nucleotide were also taken into account together with their first water shell and Na⁺ ions. We use the notation with a tilde above the abbreviation of a base for the whole nucleotide; for instance poly() means a guanine base with the deoxyribose and PO₄⁻ groups to which it is bound. The obtained band structures were compared with previous single chain calculations as well as with the earlier poly(-) and poly(-) calculation without water but in the presence of counterions. One finds that all the bands of poly(-) and poly(-) are shifted considerably upwards as compared to the previous single chain results (poly(), poly(), poly() and poly()). This effect is explained by the ∼0.2e charge transfer from the sugars of both chains to the nucleotide bases. The fundamental gaps between the nucleotide base-type highest filled and lowest unfilled bands are decreased in both cases by 1-3 eV, because the valence bands are purine-type and the conduction bands pyrimidine-type, respectively, while in the case of single homopolynucleotides they belong to the same base. We also pointed out that the LUMO is mainly Na⁺-like in both investigated cases and several unoccupied bands (belonging to the Na⁺ ions, the phosphate group and the water molecules) can be found between this and the first unoccupied pyrimidine-like empty band.     

The quark model and b baryons

The recent observation at the Tevatron of (uub and ddb) baryons within 2 MeV of the predicted Σ_b-Λ_b splitting and of baryons at the Tevatron within a few mega electron volts (MeV) of predictions has provided strong confirmation for a theoretical approach based on modeling the color hyperfine interaction. The prediction of  = 5790-5800 MeV is reviewed and similar methods used to predict the masses of the excited states and . The main source of uncertainty is the method used to estimate the mass difference m_b-m_c from known hadrons. We verify that corrections due to the details of the interquark potential and to Ξ_b- mixing are small. For S-wave qqb states we predict , and . For states with one unit of orbital angular momentum between the b quark and the two light quarks we predict , and . Results are compared with those of other recent approaches.     

Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part IV: Analysis of the absorption spectra of oxalyl fluoride in the gas phase

The gas phase absorption spectrum of oxalyl fluoride in the region of 37 000–29 300 cm⁻¹ has been examined at high resolution. Singlet–singlet and singlet–triplet electronic transitions of the trans-conformer were found in the spectrum. The fundamental frequencies of trans-oxalyl fluoride in the and electronic states were determined.In the low resolution ultraviolet absorption spectrum of oxalyl fluoride in the gas phase the transition of the cis-conformer (ν_max) was found to be shifted to the blue by about 6000 cm⁻¹ relative to the transition of the trans-conformer.     

Quantum critical behaviour in doped Y bB12 studied by ab initio calculations

The Kondo insulator Y bB₁₂ is known to undergo a transition to the metallic state with doping or under an external magnetic field. Within the virtual crystal approximation (VCA), we calculated the occupation of the Yb 4f and 5d shells, and , as a function of doping of Y bB₁₂ with the rare earths Tm and Lu. We found that exhibits an anomalous change at the critical concentration of the dopant, in agreement with experiment ( for Y b_1−xLu_xB₁₂ and for Y b_1−xTm_xB₁₂). We suggest that the critical behaviour seems to be strictly connected with the change of and in consequence the change of the Yb valency.     

Terahertz spectroscopy of oxygen, O2, in its Σg and Δ electronic states : THz Spectroscopy of O2

High precision rotational spectra of isotopic oxygen O₂ (with or ) in its electronic ground state have been measured in selected frequency regions between 0.4 and 2.0 THz. The main isotopic species, , was also investigated in its first excited electronic state . The new data, analyzed together with previous measurements, yielded improved spectroscopic parameters.     

Inelastic neutrino scattering off stable even-even Mo isotopes at low and intermediate energies

Inelastic neutrino scattering cross sections for the even-even Mo isotopes (contents of the MOON detector at Japan), at low and intermediate electron neutrino energies (?_i≤100 MeV), are calculated. MOON is a next-generation double beta and neutrino-less double-beta-decay experiment which is also a promising facility for low-energy neutrino detection. The nuclear wave functions required in this work have been constructed in the context of the quasi-particle random phase approximation (QRPA) and the results presented refer to , , , and isotopes.     

Synthesis, optical properties and crystal structures of carbazole end-capped phenylene ethynylene blue light-emitting materials

A class of highly fluorescent and stable carbazole end-capped phenylene ethynylene compounds have been synthesized and characterized. They show high extinction coefficients of absorption () and quantum yields of fluorescence (; Φ_F=0.52-0.73) in dichloromethane. The solid state absorptions and emissions are significantly red-shifted from the dilute solution ones (; ). Their photoluminescent properties and crystal structures have been investigated with the aim of providing a basis for elucidating the structure-physical property relationships. These data indicate their potential use as blue-emitting materials in organic light-emitting diodes (OLEDs).     

Time-resolved spectroscopy of Al, Ti, and Mo X pinch radiation using an X-ray streak camera

Time-resolved spectroscopic measurements of the radiation emitted from Al, Ti, and Mo X pinches have been made with time resolution. The radiation is emitted from micropinch plasmas with sizes of order in times in the 10- range. Spectra implied that dense, plasmas were produced, such as a lifetime, 1.5- electron temperature and near solid-density Ti plasma. The experimental systems and analysis methods are described in detail, including line ratio calculations for μm-scale Ti and Al plasmas with ion densities of 10¹⁹-10²⁴ cm⁻³ and electron temperatures.     

Observation of room temperature photoluminescence in proton irradiated SrTiO3 single crystal

We have irradiated SrTiO₃ single crystal with 3 MeV-proton (H⁺) beam and found that blue -, green - and infrared - frequency photoluminescence (PL) are induced simultaneously at room temperature. TEM and EELS analyses show that an oxygen-deficient amorphous layer is formed at the crystal surface by the proton irradiation. Possible origin of the PL-effect is discussed.     

Isothermal magnetic entropy behavior in Tb5Si3 : Sign reversal and non-monotonic variation with temperature, and implications

The magnetic entropy change (), a measure of the magnetocaloric effect, in Tb₅Si₃, a compound exhibiting unusual positive magnetoresistance following a magnetic-field-induced transition below the magnetic transition temperature (∼69 K), has been investigated. We found that is negative in the paramagnetic state. At the magnetic transition temperature, shows a sign reversal from a negative value (in the paramagnetic state) to a positive value (in the magnetically ordered state). The high-field state, which is interestingly the high resistive state, is found to be associated with higher entropy, i.e., large positive , behaving like a paramagnet. On the basis of this observation, we conclude that the magnetic field induces magnetic fluctuations in the system resulting in positive magnetoresistance, thereby rendering support to the idea of inverse metamagnetism in this compound. In addition, we note that the Arrott plots present an interesting scenario.     

Resonant enhancement of the formation of hydrogen-helium muonic molecules

Formation of muonic molecules and , where J is rotational quantum number, in electron conversion process is investigated at collision energies between 0.004 eV and 50 eV. Corresponding reaction rates are calculated in adiabatic approximation for the three-body Coulomb problem. Significant enhancement of the rates for and is found near 7 eV and 30 eV, respectively. It is shown that the enhancement is due to resonances present in elastic and scattering at these energies. Acceleration of dμ atoms up to the resonant energy could be realized in triple H-D-³He mixture due to the muon transfer from protium to deuterium. Experimental investigation of nuclear synthesis from molecular state directly formed in the mixture is suggested.     

Structural, elastic, electronic and magnetic properties of ThCr2Si2 from first-principles calculations

The tetragonal (s.g. I4/mmm; #139) ThCr₂Si₂ is widely known as a structural type of the broad family of the so-called 122-like ternary phases which includes now more than 800 members. Among them the superconducting iron-pnictides (discovered in 2008, -earth metals) and the newest superconducting iron-chalcogenides (discovered in 2010, metals) have attracted recently enormous interest in this class of materials. Meanwhile, the data about the electronic, magnetic, and elastic properties of the ThCr₂Si₂ phase itself are still practically absent. Here, by means of first-principles calculations, the optimized structural parameters, spin ordering of the magnetic ground state, independent elastic constants, bulk, shear, and Young’s moduli, elastic anisotropy indexes, total and partial densities of states, and inter-atomic bonding picture for ThCr₂Si₂ were obtained for the first time and analyzed in comparison with the aforementioned most popular 122-like systems and .     

Monte Carlo simulation of the compensation and critical behaviors of a ferrimagnetic core/shell nanoparticle Ising model

A Monte Carlo simulation has been used to study the magnetic properties and the critical behaviors of a single spherical nanoparticle, consisting of a ferromagnetic core of spins surrounded by a ferromagnetic shell of S=±1, 0 or , spins with antiferromagnetic interface coupling, located on a simple cubic lattice. A number of characteristic phenomena has been found. In particular, the effects of the shell coupling and the interface coupling on both the critical and compensation temperatures are investigated. We have found that, for appropriate values of the system parameters, two compensation temperatures may occur in the present system.     

Computation of energy exchanges by combining information theory and a key thermodynamic relation: Physical applications

By considering a simple thermodynamic system, in thermal equilibrium at a temperature T and in the presence of an external parameter A, we focus our attention on the particular thermodynamic (macroscopic) relation . Using standard axioms from information theory and the fact that the microscopic energy levels depend upon the external parameter A, we show that all usual results of statistical mechanics for reversible processes follow straightforwardly, without invoking the Maximum Entropy principle. For the simple system considered herein, two distinct forms of heat contributions appear naturally in the Clausius definition of entropy, . We give a special attention to the amount of heat , associated with an infinitesimal variation at fixed temperature, for which a “generalized heat capacity”, , may be defined. The usefulness of these results is illustrated by considering some simple thermodynamic cycles.