Photoemission of LaI2 and CeI2

The electronic structure of the layered compounds LaI₂ and CeI₂ was investigated by photoemission and electron energy loss spectroscopy. From the experimental results we are able to confirm the metallic nature of these compounds, and by using photon energy dependent measurements of the valence band we can identify the orbital character of the conduction band as essentially 5d¹-like. A detailed analysis of the Ce 3d and 4f spectra yields a remarkably small 4f-5d hybridization strength, almost completely decoupling the f-electron from the conduction band, which makes CeI₂ a somewhat unusual system compared to other metallic Ce compounds. Band structure calculations by Jepsen and Andersen [1] confirm these experimental results.     

V2-dependence of centrifugal constants of H2O molecules in the Morse oscillator model

It is shown in this paper that the centrifugal constantsC ^l (t) calculated in the Morse, oscillator model for the sequence from the operator H _red ^(t) , which is used in processing the rotational levels of the H₂O molecule, are linked by recurrence relations, which enables H _z ^(t) –H _z ^(O) to be given in closed form.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 56–58, October, 1982.     

Analyticity properties and a convergent expansion for the inverse correlation length of the low-temperatured-dimensional Ising model

We show that the inverse correlation lengthm(z) of the truncated spin-spin correlation function of theZ ^d Ising model with + or — boundary conditions admits the representationm(z) = –(4d–4)ln z(1–_d1) + r(z) for smallz=e ^–, i.e., large inverse temperatures is ad-dependent analytic function atz = 0, already known in closed form ford = 1 and 2; ford = 3 b_n can be computed explicitly from a finite number of the Z^d limits of z = 0 Taylor series coefficients of the finite lattice correlation function at a finite number of points ofZ ^d.     

Thermal oxidation of n-type ZnN films made by -sputtering from a zinc nitride target, and their conversion into p-type films

Transparent p-type thin films, containing zinc oxide phases, have been fabricated from the oxidation of n-type zinc nitride films. The zinc nitride thin films were deposited by rf-magnetron sputtering from a zinc nitride target in pure N₂ and pure Ar plasma. Films deposited in Ar plasma were conductive (resistivity 4.7×10⁻² Ω cm and carrier concentrations around 10²⁰ cm⁻³) Zn-rich Zn_xN_y films of low transmittance, whereas Zn_xN_y films deposited in N₂ plasma showed high transmittance (>80%), but five orders of magnitude lower conductivity. Thermal oxidation up to 550 C converted all films into p-type materials, exhibiting high resistivity, 10²–10³ Ω cm, and carrier concentration around 10¹³ cm⁻³. However, upon oxidation, the Zn_xN_y films did not show the zinc oxide phase, whereas Zn-rich Zn_xN_y films were converted into films containing ZnO and ZnO₂ phases. All films exhibited transmittance >85% with a characteristic excitonic dip in the transmittance curve at 365 nm. Low temperature photoluminescence revealed the existence of exciton emissions at 3.36 and 3.305 eV for the p-type zinc oxide film.     

q-Analogue of the Watanabe Unitary Transform Associated to the q-Continuous Gegenbauer Polynomials

We associate a family of Hilbert spaces H _q ^2;(D) of analytic functions on the unit disk D=z :|z|<1 the q-continuous Gegenbauer polynomials C _n (x;q) on the interval]–1;1[ and give a q-analogue of the unitary integral transform that Watanabe constructed from the Hilbert space L ²(]–1;1[;(1–x ²)^– dx onto the weighted Hilbert space H ^2;(D).     

Dielectric/piezoelectric properties and temperature dependence of domain structure evolution in lead free single crystal

(K_0.5Na_0.5)NbO₃ (KNN) single crystals were grown using a high temperature flux method. The dielectric permittivity was measured as a function of temperature for [001]-oriented KNN single crystals. The ferroelectric phase transition temperatures, including the rhombohedral–orthorhombic T_R−O, orthorhombic–tetragonal T_O−T and tetragonal–cubic T_C were found to be located at −149  C, 205 C and 393 C, respectively. The domain structure evolution with an increasing temperature in [001]-oriented KNN single crystal was observed using polarized light microscopy (PLM), where three distinguished changes of the domain structures were found to occur at −150  C, 213 C and 400 C, corresponding to the three phase transition temperatures.     

Laser-induced fluorescence detection of singlet CH2 in low-pressure methane/oxygen flames

Methylene, CH₂, is a chemically important intermediate in hydrocarbon combustion but has previously eluded optical detection in a combustion environment. The CH₂ signal as a function of height above the burner surface in a premixed, laminar, methane/oxygen flame (5.6 Torr and fuel equivalence ratio 1.05) is measured by laser-induced fluorescence (LIF) in the B ₁ – ã¹ A ₁ electronic system. The ã state which lies 3165 cm^–1 above the ground state is populated at the high temperatures of the flame (800–1800 K). Although less than one photon for each laser pulse is detected, we can unambiguously attribute the LIF features in the region 450 to 650 nm to CH₂ by both scanning the excitation laser and dispersing fluorescence. LIF temperatures and CH and OH LIF concentration profiles are also obtained for the flame. The CH₂ radical concentration maximum occurs closer to the burner than that of either OH or CH, as expected from models of methane combustion chemistry.     

Solubility of Na2Co3 in NaCl:CaCl2 crystals

Measurements of electrical conductivity of NaCl 10^–5 molar fr. CaCl2 (1–80)×10^–5 molar fr. Na₂CO₃ crystals have been used to determine the temperature dependence of the solubility of CO₃-ions over the temperature range from 75 to 530 °C. The total solubility of CO₃-ions and that of [CO ₃ ^2– -vacancy] complexes may be expressed by simple relationships andc _ka=3·19× 10^–2 exp (–0·25 eV/kT), resp. The heat of solution of complexes is equal to 0·25 eV and that of free CO ₃ ^2– ions is higher than 1·2 eV. Under conditions of the thermal equilibrium between the solid solution and precipitate, the ratio of Na₂CO₃ and CaCO₃ components in the precipitate has been calculated at various temperatures and CO₃ concentrations.     

Negative-ion photoelectron spectroscopy of acrylonitrile clusters containing a sodium atom

Cluster anions of a sodium atom with acrylonitrile molecules, (n = 0–6), have been studied by negative-ion photoelectron spectroscopy. In addition, theoretical calculations by using density functional theory have been performed to obtain optimized structures and vertical detachment energies. For Na(AN)^–, the spectrum can be explained by excitation of two different isomers of the anion. For , a broad band is found in the photoelectron spectrum, whose profile is almost identical with those of previously reported photoelectron spectra of and a negative ion of chemically synthesized 1,3,5-cyclohexanetricarbonitrile (CHTCN) molecule. From this resemblance of band profiles, we conclude that oligomerization of (AN)₃ takes place in and the CHTCN is formed as the intracluster reaction product.     

Photoluminescence of AlxGa1−xAs/GaAs quantum well heterostructures grown by molecular beam epitaxy

Low-temperature photoluminescence measurements on nominally undoped Al_xGa_1–xAs/GaAs quantum well heterostructures (QWHs) grown by molecular beam epitaxy (MBE) exemplified the exclusivelyintrinsic free-exciton nature of the luminescence under moderate excitation conditions. Neither any spectroscopic evidence for alloy clustering in the Al_xGa_1–xAs barriers nor any extrinsic luminescence due to recombination with residual acceptors has been detected in single and double QWHs when grown at 670 °C under optimized MBE growth conditions. Carrier confinement in Al_xGa_1–xAs/GaAs QWHs starts at a well width ofL _z30 nm when x0.25. The minor average well thickness fluctuation ofL _z=4×10^–2nm as determined from the excitonic halfwidth allowed the realization of well widths as low asL _z=1 nm and thus a shift of the free-exciton line as high as 2.01 eV which is close to the conduction band edge of the employed Al_0.43Ga_0.57As confinement layer. The measurements further revealed a strongly enhanced luminescence efficiency of the quantum wells as compared to bulk material which is caused by the modified exciton transition probabilities due to carrier localization.     

Synthesis and superconductivity of a new 1222-type T1-based layered cuprate (T1, Nb) Sr2(Nd,Ce)2Cu2O z

Synthesis and superconductivity of a new 1222-type layered cuprate (Tl_1–x Nb _x ) Sr₂(Nd_1–y Ce _y )₂Cu₂O _z have been studied. The structure of this cuprate is directly related to that of Nb-1222 NbSr₂(Nd, Ce)₂Cu₂O _z with tetragonal body-center lattice. Partial substitution of Tl for Nb in Nb-1222 phase improves its superconductivity. (Tl_1–x Nb _x ) Sr₂(Nd_0.75Ce_0.25)₂Cu₂O _z samples prepared by the typical procedure exhibit superconductivity withT _c of 30–40 K. Effects of Tl and Nb on superconductivity of this cuprate are briefly discussed.     

The ESR spectrum of oxygen vacancies in sodium tellurite glasses

A theoretical analysis is presented for the shape of the ESR spectrum of the radiation-induced centers of oxygen vacancy type in sodium tellurite glasses. It is found that a qualitative agreement between the theoretical and observed curves can be obtained only if one assumes a completely anisotropic g factor and an inhomogeneous structure for the paramagnetic centers, whose parameters are found as g_x = 1.930; g_y = 1.971; g_z = 2.046; x ² >=4–10^–4-2.5·10^–3; y ² > = 4.9·10^–8-1·10^–6; z ² > = 2.2·10^–4-9·10^–4; d ² > = 36–100 G². It is concluded that the glass composition affects the center nonuniformity.Translated from Izvestiya VUZ, Fizika, No. 3, pp. 63–68, March, 1973.     

Thermal equilibrium concentrations and effects of negatively charged Ga vacancies in n-type GaAs

We have calculated the thermal equilibrium concentrations of the various negatively charged Ga vacancy species in GaAs. The triply-negatively-charged Ga vacancy, V _Ga ^3– , has been emphasized, since it dominates Ga self-diffusion and Ga-Al interdiffusion under intrinsic and n-doping conditions, as well as the diffusion of Si donor atoms occupying Ga sites. Under strong n-doping conditions, the thermal equilibrium V _Ga ^3– concentration, , has been found to exhibit a temperature independence or a negative temperature dependence, i.e., the value is either unchanged or increases as the temperature is lowered. This is quite contrary to the normal point defect behavior for which the point defect thermal equilibrium concentration decreases as the temperature is lowered. This property provides explanations to a number of outstanding experimental results, either requiring the interpretation that V _Ga ^3– has attained its thermal equilibrium concentration at the onset of each experiment, or requiring mechanisms involving point defect non-equilibrium phenomena.     

Diffusive EPR line width behaviour in two-dimensional Cu(Hippurate)2 4H2O single crystal

X-band EPR measurements were performed at room temperature on layered Cu(Hippurate)₂4H₂O single crystals. Despite the dimeric molecular structure the EPR spectra are characteristic for individual Cu-complexes with square-pyramidal structure and g-factors: g_x=2.045, g_y=2.085 and g_z=2.346. The anticipated zero-field splitting from dimers with S=1 is averaged out by interdimer exchange coupling within the layers. The dimers in adjacent layers are not exchange coupled as we determined from the two-component EPR spectra. Thus, the crystal is an ideal 2D magnetic system and shows a strong spin diffusion effect in the EPR line width. The spin diffusion contribution to the line width is described as P(3cos²Θ−1)² with which is much higher compared to other 2D copper(II) crystals. The background line width is due to dipolar coupling and non-resolved hyperfine structure. Exchange coupling was determined from the exchange narrowing effect as of about 0.1 cm⁻¹.     

Masses ofq 2 \bar q 2 states in a Bethe-Salpeter model

Ground-state masses ofq ^{2 –2} states (true and mock baryonium) are investigated in the framework of a Bethe-Salpeter formalism motivated from QCD. The four-particle system is described by pairwise interactions betweenqq orq pairs with a spectator approximation for the non-interacting pair. The quark-quark interactions are Coulomb plus harmonic interactions; the harmonic terms have been modified to produce linear confinement for heavier quarks, in agreement with experimental spectra. The confining interaction is proportional to the strong coupling constant _s. Apart from the quark masses, the confining interaction is characterized by three basic parameters: (i) a universal spring constant ₀; (ii) a constantC ₀/ ₀ ² , which defines the vacuum structure; (iii) a constantA ₀, which provides a smooth transition from quadratic to linear confinement as one goes from light to heavy quark systems. These three constants [ ₀ = 0.158 GeV;C ₀=0.296;A ₀=0.0283] have been shown to produce excellent fits to all quarkonia states [q ,q ,Q ] as well as baryon spectra (qqq); thus our predictions forq ^{2 2} states contain no free parameters. In this model, theL=0 ground states occur in the range 1.8–2 GeV, 2.15–2.3 GeV and 6.72–6.75 GeV foru ^{2 2},s ^{2 2} andc ^{2 2} states, respectively. We discuss the prospects for these states to be seen experimentally. In the case of thes ^{2 2} state, this is likely to have a rather narrow width, and may correspond to theX(2.22 GeV) meson observed in radiative decays of theJ/ meson. Thec ^{2 2} state might also be visible as a resonance with an appreciable width.Research supported in part by the National Science Foundation under grant NSF-PHY 86-06364Research supported in part by the U.S. Department of Energy     

Single crystal EPR spectrum of Cr3+ in lanthanum lutecium gallium garnet

The Cr³⁺ EPR spectra of YAG type crystals normally consist of four peaks whose positions are dependent on the axial zero-field splitting D with axis along a 111 direction and angle between that direction and the applied field H ₀. In LLGG only three principal peaks are observed with zero-field axis nearly along x, y or z. This anomaly is attributed to the relatively small size of Cr³⁺ compared to Lu³⁺ which it displaces in an octahedral site. D varies slightly for the different zero-field axes: 0.480 cm^–1 along x, 0.429 cm^–1 along y and 0.470 cm^–1 along z. The spectroscopic splitting factor g=1.978±0.001 is essentially isotropic and independent of axes within the experimental error.     

Instability of the molecular structure of monobenzoporphin to the alternation of the macrocycle bond lengths and its manifestation in the electronic spectra

Quantum-chemical calculations of the geometric structure of the molecules of monobenzoporphin (H₂ MBP) and monobenzoporphin with methyl and ethyl substituents in the five-member rings (H₂MBPm) have been carried out by the restricted and unrestricted Hartree-Fock methods with the AM1 Hamiltonian (AM1 RHF and AM1 UHF methods). The calculation of the above-indicated molecules by the AM1 RHF method without restrictions on their symmetry has given, for them, a planar structure with an alternation of the lengths of the bonds along the 18-member azacyclopolyene and the symmetry C _1h for their aromatic part. The calculation of the transitions to the excited electron Q states in such a structure by the CNDO/S method has shown that these states are characterized by large hypsochromic shifts (~3000–4000 cm^–1 ) relative to the Q levels of porphin (H₂P), which is in contradiction with the experimental data, according to which these shifts are bathochromic and comprise = –330 cm ^–1 and = –750 cm^–1. Optimization of the geometry of the H₂ MBP and H₂MBPm molecules by the AM1 UHF method gives, for them, a structure with equal lengths of the bonds along the 18-member azacyclopolyene with a symmetry differing insignificantly from the D _2h symmetry; elements of the structure with a lower symmetry and an alternation of the lengths of the bonds are retained in the condensed pyrrolenine and benzene rings. The calculation of the shifts of the Q levels in the H₂MBPm molecule of this geometry relative to the analogous levels in H₂P has shown that they are bathochromic and equal to = –520 cm^–1, and the RHF calculation with optimization of the geometry of the molecule and restrictions on the effective symmetry D _2h of the 18-member azacyclopolyene has given = –350 cm^–1 and = –430 cm^–1. The restrictions imposed on the C ₂ symmetry of the H₂MBP molecules by the RHF method are inadequate to equalize the lengths of the bonds along the 18-member azacyclopolyene. The calculations of the energy of the B levels of the monobenzoporphyrins considered also lend credence to their geometric structure with equal lengths of the bonds along the 18-member azacyclopolyene.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 712–721, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Ab Initio Study of the Phosphorescence of Nitrite Ions

In order to interpret the phosphorescence spectra of NaNO₂ and similar single crystals, we performed MCSCF geometry optimization in the ground singlet (X ¹ A ₁) and in the first excited triplet (a ³ B ₁) states of the NO ₂ ^- ion and MCSCF quadratic response (QR) calculation of the a ³ B ₁–X ¹ A ₁ transition probability at different bending angles and asymmetric stretch modes. The complete form of the spin–orbit coupling (SOC) operator is accounted for in the QR procedure. Dunning's correlation-consistent polarized valence double- (cc-pVDZ) and triple- (cc-pVTZ) basis sets are imployed. The electric-dipole transition moment from the T ^z spin sublevel (z is the C ₂ axis) oriented along the y direction (the other in-plane axis) is found to be 5 times higher than that from the T ^y sublevel in the ground-state geometry. This is in agreement with polarization measurements and with optical detection of ESR spectra. The T ^z–S ₀ transition moment decreases almost linearly with an increase in the ONO bond angle. The so-called non-Condon effects in the phosphorescence spectra of NaNO₂ crystals are explained on these backgrounds. The long progression of the bending vibrations (v ₂, a ₁) with an anomolous intensity distribution in the T ^z–S ₀ transition and additional involvement of the asymmetric stretch mode (v ₃, b ₂) in the T ^y–S ₀ transition are interpreted by force field and SOC calculations in the MCSCF-response technique. Configuration interaction (CI) calculations of the spin-allowed electric dipole transitions in NO ₂ ^- ions with effective one-electron SOC operator matrix element estimations were done for comparison with the results of the quadratic and linear response methods. Other T _n–S ₀ transitions are also studied. Finally, a short discussion of nonradiative processes is presented.     

A differential technique to measure small product yield increments in a time-of-flight mass spectrometer for investigating IR spectra of highly excited polyatomics

We present an experimental technique for measuring small product yield increments in a specially designed time-of-flight mass spectrometer with a supersonic jet. Advantages of this technique are demonstrated in measuring the photodissociation IR spectrum (990–1050 cm^–1) of CF₃I molecules with vibrational energy at the threshold value. The differential technique has enabled us to reveal an anomalously narrow width of the spike of thev ₁ band of CF₃I. We discuss this anomaly.     

Infrared multiple photon dissociation spectroscopy of transition metal oxide cluster cations

Infrared spectra in the range of 530–1400 cm^–1 are presented for tantalum oxide cluster cations (x = 3, 4 and 6). These spectra are obtained via multiple photon dissociation (MPD) spectroscopy of free cluster cations moving in a molecular beam. The IR spectra for are compared to spectra of as well as to the experimental data available for vanadium oxide cluster cations from IR-MPD spectroscopy. For and the IR spectra exhibit very strong similarities (including the band positions), whereas absorption bands in are relatively blue-shifted by about 20–40 cm^–1.