Origin of the 330 nm absorption band and effect of doping Yb in LiYF4 crystals

The electronic structures of LiYF₄ (YLF) crystals containing F color center (YLF-F) and Yb doped YLF crystals (Yb³⁺:YLF, Yb²⁺:YLF) are systematically studied within the framework of the density functional theory. The calculated results indicate that the 330 nm absorption band originates from the F center in YLF crystals. Thus the doping of Yb³⁺ can weaken the 330 nm absorption band by competing with F vacancies in capturing free electrons arising after γ-irradiation and change to Yb². By analyzing the lattice relaxation and the electronic structure of YLF containing Yb²⁺, we can reasonably believe that once Yb²⁺ is formed in YLF crystal, its compensating hole will turn out to be shared by two F⁻ nearest to Yb²⁺ forming a diatomic fluoride molecular ion () perturbed by Yb²⁺, or to say V_F color center. According to the molecular-orbital linear combination of atomic orbital (MO-LCAOs) theory, compared to the alkali halides, e.g. LiF, the in V_F center in LiYF₄ peaks at about 340 nm, which is in agreement with the experimental results.     

Absorption spectra of AsH2 radical in 435-510 nm by cavity ringdown spectroscopy

The absorption spectra of jet-cooled AsH₂ radicals were recorded in the wavelength range of 435-510 nm by cavity ringdown spectroscopy. The AsH₂ radicals were produced by pulsed DC discharge in a molecular beam of a mixture of AsH₃, SF₆, and argon. Seven vibronic bands with fine rotational structures have been identified and assigned as the , , and (n = 1-3) bands of the electronic transition. Based on the previous studies of AsH₂ radical, rotational assignments and rotational term values for each band were obtained, and the molecular parameters including vibrational constants, rotational constants, centrifugal distortion constants, and spin-rotation interaction constants were also determined.     

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.     

Diode laser spectroscopy of ammonia at 760 nm

A tunable diode laser spectrometer has been employed to examine the unknown overtone absorption lines of NH₃ around (760 nm). The spectrometer sources are commercially available heterostructure AlGaAs tunable diode lasers operating in the “free-running” mode. The detection of the lines has been possible by the use of the wavelength modulation spectroscopy and the second harmonic detection technique. A special algorithm has been used in order to fit the highly modulated absorption lines. The weakest observed resonances have absorption cross sections on the order of ?/molecule or ?/amagat. For some of the more intense lines self-, air-, N₂-, He- and H₂-broadening coefficients have been obtained at room temperature and also some shifting coefficients have been measured.     

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.     

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.     

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.     

High-temperature UV absorption of methyl radicals behind shock waves

The absorption of ultraviolet narrow-line laser radiation by methyl radicals (CH₃) in the electronic system has been studied at high temperatures behind shock waves. Methyl radicals at high temperatures were generated by the shock heating of methyl precursors: azomethane, methyl iodide, and ethane. The spectral shape and intensity of the broadband absorption feature from 211.5 to 220 nm at high temperature (1565 K) has been measured. The absorption coefficient of CH₃ at 216.62 nm, the wavelength of peak absorption at high temperatures in the P+Q band, has been determined from 1200 to 2500 K. Additionally, the absorption coefficients of several interfering UV-absorbing combustion species (, and C₃H₆) have been determined at 216.62 nm.     

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.     

Possible coexistence of superconductivity and magnetism in intermetallic NiBi3

NiBi₃ polycrystals were synthesized via a solid state method. X-ray diffraction analysis shows that the main phase present in the sample corresponds to NiBi₃ in a weight fraction of 96.82 % according to the refinement of the crystalline structure. SEM - EDS and XPS analysis reveal a homogeneous composition of NiBi₃, without Ni traces. The powder superconducting samples were studied by performing magnetic measurements. The superconducting transition temperature and critical magnetic fields were determined as , Oe and Oe. The superconducting parameters were , , and κ=5.136. Isothermal measurements below the transition temperature show an anomalous behavior. Above the superconducting transition the compound presents ferromagnetic characteristics up to 750 K, well above the Ni Curie temperature.     

Electronic and elastic properties of a double perovskite slab-rocksalt layer of Eu2SrAl2O7 investigated by LSDA+U

The electronic structure and elastic properties of a double perovskite slab-rocksalt layer compounds of Eu₂SrAl₂O₇ were calculated by local- (spin-) density approximation [L(S) DA] band theory with Hubbard term of U. We used and for the calculations. The band gap of Eu₂SrAl₂O₇ is 4.8 eV. Both of Eu-O and Al-O bonds have strong covalent character and Sr-O is a perfect ionic bond. The full set elastic constants indicate the elastic modulus of Eu₂SrAl₂O₇ is 224 and 240 GPa by calculation and experiment, respectively.     

Multiple superconducting gap and anisotropic spin fluctuations in iron arsenides: Comparison with nickel analog

We present extensive ⁷⁵As NMR and NQR data on the superconducting arsenides PrFeAs_0.89F_0.11, LaFeAsO_0.92F_0.08, LiFeAs and Ba_0.72K_0.28Fe₂As₂ single crystal, and compare with the nickel analog LaNiAsO_0.9F_0.1. In contrast to LaNiAsO_0.9F_0.1 where the superconducting gap is shown to be isotropic, the spin lattice relaxation rate 1/T₁ in the Fe-arsenides decreases below T_c with no coherence peak and shows a step-wise variation at low temperatures. The Knight shift decreases below T_c and shows a step-wise T variation as well. These results indicate spin-singlet superconductivity with multiple gaps in the Fe-arsenides. The Fe antiferromagnetic spin fluctuations are anisotropic and weaker compared to underdoped copper-oxides or cobalt-oxide superconductors, while there is no significant electron correlations in LaNiAsO_0.9F_0.1. We will discuss the implications of these results and highlight the importance of the Fermi surface topology.     

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 .     

Ac magnetotransport in La0.7Sr0.3Mn0.95Fe0.05O3 at low dc magnetic fields

We report the ac electrical response of La_0.7Sr_0.3Mn_1−xFe_xO₃(x=0.05) as a function of temperature, magnetic field (H) and frequency of radio frequency (rf) current (). The ac impedance (Z) was measured while rf current directly passes through the sample as well as in a coil surrounding the sample. It is found that with increasing frequency of the rf current, Z(T) shows an abrupt increase accompanied by a peak at the ferromagnetic Curie temperature. The peak decreases in magnitude and shifts down with increasing value of H. We find a magnetoimpedance of for at around room temperature when the rf current flows directly through the sample and when the rf current flows through a coil surrounding the sample. It is suggested that the magnetoimpedance observed is a consequence of suppression of transverse permeability which enhances skin depth for current flow. Our results indicate that the magnetic field control of high frequency impedance of manganites is more useful than direct current magnetoresistance for low-field applications.     

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.     

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.     

Shape-dependent local internal stress of α-Cr2O3 nanocrystal fabricated by pulsed laser ablation

The α-Cr₂O₃ single-crystal nanocondensates were fabricated by pulsed laser ablation in air and characterized by analytical electron microscopy regarding shape-dependent local internal stress of the anisotropic crystal. The nanocondensates formed predominantly as rhombohedra with well-developed surfaces and occasionally hexagonal plate with thin edges and blunt corners. Such nanocondensates showed Raman shift for the CrO₆ polyhedra, indicating a local compressive stress up to ca. 4 GPa on the average. Careful analysis of the lattice fringes revealed a local compressive stress (0.5% strain) at the thin edge of the hexagonal plates and a local tensile stress (0.3–1.0% strain) near the relaxed , , and (0 0 0 1) surfaces of truncated rhombohedra. The combined effects of nanosize, capillarity force at sharp edge, and specific surface relaxation account for the retention of a local internal compressive stress built up in an anisotropic crystal during a very rapid heating–cooling process.     

Ultraviolet absorption spectrum and cross-sections of ethynyl (C2H) radicals

This work reports the ultraviolet absorption spectrum and cross-sections of ethynyl (C₂H) radicals in the wavelength range 235-260 nm, determined at T=298 K and at a total pressure of about 20 kPa (150 Torr). Ethynyl radicals were produced from the single photon 193 nm excimer laser photolysis of dilute mixtures of C₂HCF₃ or C₂H₂ in He. Gas chromatographic/mass spectroscopic analysis of the photolyzed samples showed diacetylene (C₄H₂) as the major stable product. Addition of methane in the photolysis mixtures resulted in reduction of diacetylene and production of methylacetylene and ethane, products of the reaction of ethynyl radicals with methane. Survey of the ultraviolet spectral region, employing time-resolved UV-absorption spectroscopy, resulted in detection of a transient absorption centered at about 243 nm. The spectra obtained from the 193-nm photolysis of both C₂HCF₃/He and C₂H₂/He radical precursors were nearly identical, suggesting that the absorption feature can be attributed to the ethynyl radicals. The observed ultraviolet spectrum exhibits a relatively broad absorption feature with some structures and an absorption peak at about 243.5 nm. The absorption cross-sections for ethynyl radicals have been determined in this work for the first time. The C₂H cross-section, at the maximum absorption, at 243.5 nm is . The stated uncertainty includes the random and systematic measurement errors. The UV absorption feature, detected in this work, can be assigned to the transitions from the ground electronic state and also possibly from coupled ground and lowest electronic states to the electronic state B (or 32A′) of C₂H. This assignment is based on previously reported high level ab initio molecular orbital calculations and results of recent laser-induced fluorescence studies of the ethynyl radical.     

Electronic absorption spectra of CCS and CCS in neon matrices

Mass selected C₂S⁻ ions have been co-deposited with neon to grow a matrix at 6 K. The and electronic absorption spectra of the linear CCS⁻ anion have been identified with origin band at 10 606 and 22 273 cm⁻¹, respectively. After exposure to UV radiation a new electronic transition of CCS is observed (origin band at 30 563 cm⁻¹) in addition to its known band system. Ab initio calculations provide support for the symmetry assignment of the upper electronic states of CCS⁻, CCS and of the vibrational structure in the spectra.     

First principle study of the electronic and magnetic properties of a single iron atomic chain encapsulated in boron nitrite nanotubes

The electronic and magnetic properties for a single Fe atom chain wrapped in armchair (n,n) boron nitride nanotubes (BNNTs) (4≤n≤6) are investigated through the density functional theory. By increasing the nanotube diameter, the magnetic moments, total magnetic moments and spin polarization of systems are increased. We have calculated the majority and minority density of states (DOS) of armchair BNNT. Our results show that the magnetic moment of the system come mostly from the Fe atom chain. The magnetic moment on an Fe atom, the total magnetic moment and spin polarization decrease by increasing the axial separation of the Fe atom chain for the system. The BNNT can be used in the magnetic nanodevices because of higher magnetic moment and spin polarization.