Millimeter-wave spectrum of Ne–CO: new measurements

The b-type rotational transitions of the van der Waals complex, Ne–CO have been measured using the intracavity OROTRON jet spectrometer in the frequency range of 80–115 GHz. The high sensitivity of this technique enabled us to detect all three Ne isotopic modifications of the complex, ²⁰Ne–CO, ²²Ne–CO, and ²¹Ne–CO in natural abundance. The observed and assigned transitions belong to the Q-branch of the K = 1–0 subband and include also R (0) and P (2) lines. The newly obtained data were analysed together with previously observed millimeter-wave b-type and microwave a-type rotational transitions.     

Rotational spectrum of the Ar–dimethyl sulfide complex

The rotational spectra of three isotopomers of the Ar–dimethyl sulfide (DMS) complex – normal, ³⁴S, and ¹³C species – were measured in the frequency region from 3.7 up to 24.1 GHz by Fourier transform microwave spectroscopy. The normal species yielded 43 a-type and 79 c-type transitions. No Ar tunneling splitting was observed, while many transitions were split by the internal rotation of the two methyl tops of the DMS unit. In cases where the K-type splitting was close to that due to methyl internal-rotation, several forbidden transitions were observed that followed b-type selection rules. All of the observed transition frequencies were analyzed simultaneously using a phenomenological Hamiltonian also used in previously published work describing the Ar–dimethyl ether (DME) and Ne–DME complexes. The rotational and centrifugal distortion constants and the potential barrier height to methyl-top internal rotation, V₃, were determined. The rotational constants were consistent with an Ar–DMS center of mass (cm) distance of 3.796 (3) Å and a S–cm–Ar angle of 104.8 (2)°. The V₃ potential barrier obtained, 736.17 (32) cm⁻¹, was 97.8% of the DMS monomer barrier. By assuming a Lennard–Jones-type potential, the dissociation energy was estimated to be 2.4 kJ mol⁻¹, which was close to the value for Ar–DME, 2.5 kJ mol⁻¹.     

The Electric Dipole Moment of the CO2–CO van der Waals Complex

Radiofrequency transitions withinK= 2 asymmetry doublets have been observed for the CO₂–CO van der Waals complex. A Stark effect measurement on theJ= 2,K= 2 transition provides an electric dipole moment of μ = 0.2493(1) D. Combining this result with the permanent moment of CO, μ_CO= 0.1098 D, gives a change of moment on complex formation of Δμ = 0.140 D. The sign of Δμ is such that the CO end of the complex is more positive than CO₂. The origin of Δμ should not be attributed to any single mechanism, and several different contributions to Δμ are discussed.     

Bond operator theory for the frustrated anisotropic Heisenberg antiferromagnet on a square lattice

The quantum anisotropic antiferromagnetic Heisenberg model with single ion anisotropy, spin S=1 and up to the next-next-nearest neighbor coupling (the J₁–J₂–J₃ model) on a square lattice, is studied using the bond-operator formalism in a mean field approximation. The quantum phase transitions at zero temperature are obtained. The model features a complex T=0 phase diagram, whose ordering vector is subject to quantum corrections with respect to the classical limit. The phase diagram shows a quantum paramagnetic phase situated among Neél, spiral and collinear states.     

An ab initio study of the Ne-CO complex

A new ab initio potential energy surface of the Ne-CO complex is developed using single and double excitation coupled-cluster theory with noniterative treatment of triple excitations [CCSD(T)].The potential has a minimum value of 49.396 cm 1 at R e = 6.40a 0 with approximately T-shaped geometry(θ e = 82.5).Bound state energies are calculated up to J = 12.The theoretically predicted transition frequencies and spectroscopic constants are in good agreement with the available experimental results.     

Can electron paramagnetic resonance measurements predict the electrical sensitivity of SnO<Subscript>2</Subscript>-based film?

Paramagnetic singly ionized oxygen vacancies V_o and chemisorbed Sn⁴⁺-O₂⁻ species were detected by electron paramagnetic resonance measurements on SnO₂ and transition metal (Pt, Ru)-doped SnO₂ thin film that had been reduced with CO at different temperatures and then brought into contact with oxygen. The amounts of the two paramagnetic species were evaluated and are discussed as a function of the film annealing temperature in air, the reduction temperature under CO, and the type and concentration of the doping transition element. Also the structural properties of the film were identified through glancing incidence X-ray diffraction analysis. Measurements of the electrical sensitivityS(S=R _air/R _CO, whereR _air andR _CO are the resistance under air and under CO(800 ppm)/air respectively) show that the trend of the sensitivity values vs. the reduction temperature with CO could be predicted by the parallel trend of the number of Sn⁴⁺−O₂⁻ centers.     

The problem of the structure (state of helium) in small He<Subscript><Emphasis Type="Italic">N</Emphasis></Subscript>-CO clusters

A second-order perturbation theory, developed for calculating the energy levels of the He-CO binary complex, is applied to small He _N -CO clusters with N = 2−4, the helium atoms being considered as a single bound object. The interaction potential between the CO molecule and HeN is represented as a linear expansion in Legendre polynomials, in which the free rotation limit is chosen as the zero approximation and the angular dependence of the interaction is considered as a small perturbation. By fitting calculated rotational transitions to experimental values it was possible to determine the optimal parameters of the potential and to achieve good agreement (to within less than 1%) between calculated and experimental energy levels. As a result, the shape of the angular anisotropy of the interaction potential is obtained for various clusters. It turns out that the minimum of the potential energy is smoothly shifted from an angle between the axes of the CO molecule and the cluster of θ = 100° in He-CO to θ = 180° (the oxygen end) in He₃-CO and He₄-CO clusters. Under the assumption that the distribution of helium atoms with respect to the cluster axis is cylindrically symmetric, the structure of the cluster can be represented as a pyramid with the CO molecule at the vertex.     

The First Excited Ca–C–C Bending Vibration Levels in theÃΠ andXΣStates of the CaCCH Radical: The Renner–Teller Effect andK-type Resonance

The 5¹₀and 5¹₁bands of the CaCCHÃ²Π–X²Σ⁺transition, corresponding to the Ca–C–C bending mode, have been rotationally analyzed through cw dye laser excitation and dispersed fluorescence with a CCD array detector. The upper state is subject to Renner–Teller and spin–orbit couplings, and strongK-type resonance interactions were observed between the nearby²Δ and²Σ vibronic components. A model that invokes a full matrix treatment of these interactions was employed in a least-squares fit of a total of 708 rotational lines of the two bands, recorded with high precision. The fundamental bending frequencies have been determined as ν₅= 101.394(1) and 102.940(1) cm⁻¹for theÃ²Π andX²Σ⁺electronic states, respectively. The Renner–Teller parameter has been determined as ?₅ω₅= 3.528(14) cm⁻¹. The nonadiabatic parameter for the ν₅mode,g_K= 0.6542(10) cm⁻¹, is in accord with the observation that the²Δ_5/2vibronic component liesabovethe normally highest κ²Σ component.     

Structural study and electrical properties of Zr-doped Nd<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript> pyrochlore compounds

Nd₂Sn₂O₇ pyrochlores with the substitution of Zr⁴⁺ were prepared by conventional ceramic double sintering technique. The single-phase formation was confirmed by X-ray diffraction and neutron diffraction techniques. Relative intensity calculations for X-ray diffraction analysis were performed for oxygen positional parametersx = 0.331 and 0.375, while Rietveld refinements were employed for neutron diffraction data. The neutron diffraction study revealed that there are only two anion sites with 48f and 8b positions. This indicates that the 8a site, i.e. O(3) sublattice, is completely vacant and the structure is a perfect cubic pyrochlore with space group Fd3m (O _h ⁷ ). From the conductivity measurements, it is observed that the electronic conductivity dominates from room temperature up to about 525 K and forT > 525 K, the oxygen ion conduction dominates the charge transport in these compositions. Complex impedance spectroscopy indicates the existence of grain and grain boundary as two separate elements.     

Infrared spectra of acetylene dimers and acetylene–nitrogen: (DCCD)2, H-bonded DCCD–HCCH, and DCCD–NN in the 4.1 μm region

Infrared spectra of the weakly-bound T-shaped acetylene dimers DCCD–DCCD and DCCD–HCCH are studied in the region of the DCCD ν₃ fundamental (∼2440 cm⁻¹) using a pulsed supersonic slit-jet expansion and a tunable diode laser probe. The K_a = 0 ← 1 and 1 ← 0 subbands, corresponding to the vibration of the DCCD monomer at the “top” of the T, are analyzed. Compared to the analogous spectrum of HCCH–HCCH, the present results are much less perturbed. The tunneling splitting for (DCCD)₂ in the excited state is determined to be 141 MHz, a big reduction from the previously determined ground state value of 424 MHz. The dimer A rotational constants show a large apparent increase upon vibrational excitation, and we discuss whether this increase is real. The linear DCCD–NN complex is also observed as an impurity in the spectrum, and it too is found to be unperturbed, in contrast with HCCH–NN.     

N2Broadening in theCO 2–0 Band around 4167 cm

N₂broadening coefficients have been measured for 65 lines of the¹³C¹⁶O 2–0 band using a Fourier transform spectrometer. These lines are located in the spectral range 4011–4252 cm⁻¹. The spectra were recorded with 99% isotopically pure¹³CO in a White-type cell at a resolution of 0.005 cm⁻¹. Voigt profiles convolved with the FTS apparatus function were fitted to the experimental lineshapes using a nonlinear least-squares fit technique. From the fits the Lorentzian HWHM was determined as function of N₂pressure. Pressure broadening coefficients formbetween −33 and +34 were obtained with uncertainties of 5.8%. The results are compared to earlier published N₂broadening coefficients and our measurements in the 2–0 band of¹²C¹⁶O. To our knowledge this is the first investigation of¹³CO pressure broadening.     

Infrared spectra of the Kr—CO and Xe—CO van der Waals complexes

The infrared spectra of the weakly bound complexes Kr—CO and Xe—CO have been studied in the region of the CO stretching vibration (4.7 μm) using a high-resolution tuneable diode laser probe. The complexes were observed in a long path (200 m) low temperature (76 K) gas cell (Kr—CO) and in a pulsed supersonic jet expansion (Kr—CO and Xe—CO). Previous long path cell measurements on these complexes at lower resolution analysed only the K = 0 and 1 stacks of rotational levels in the ground intermolecular vibrational state. The new data extend up to K = 3 (Xe—CO) or 4 (Kr—CO), and also include K = 0 and 1 stacks in the excited bending state, ν₂ = 1. The bending frequencies for Kr—CO and Xe—CO (in the ν_co = 1 upper state) were determined to be 13.156cm_?1 and 13.794cm^?1, respectively. Detailed molecular parameters were determined to describe the rotational energy levels of each complex using a simple empirical Hamiltonian. These results enable parameters to be compared for the entire series of rare gas—carbon monoxide complexes, from He—CO to Xe—CO. Also they will guide the future development and evaluation of accurate intermolecular potential energy surfaces for Kr—CO and Xe—CO.     

The glassy state of the amorphous V2O5–NiO–TeO2 samples

The glass transition temperature dependence to heating rate and therefore the activation energy (ΔH^?) of the glass transition of (60-x)V₂O₅–xNiO–40TeO₂ oxide glasses with 0≤x≤20 (in mol%) were investigated at heating rates φ (=3 6, 9, 10 and 12 K/min) using differential scanning calorimetry (DSC). The heating rate dependence of T_g was used to investigate the applicability of different theoretical models describing the glass transition. Using the application of Moynihan and Kissinger et al. models to the present data, different values of (ΔH^?) at each different heating-rate regions were obtained. The fragility parameter (m=ΔH^?/R T_g) was ∼24.98 for x=10 mol%, suggesting that this glass may be considered as a rather strong glass (fragility index m∼>20 is an indication of fragile glass). Also the compositional dependence of T_g and ΔH^? was investigated.     

Properties of nanocrystalline Al–Cu–O films reactively sputtered by DC pulse dual magnetron

The article reports on the effect of the addition of copper in the Al₂O₃ film on its mechanical and optical properties. The Al–Cu–O films were reactively co-sputtered using DC pulse dual magnetron in a mixture of Ar + O₂. One magnetron was equipped with a pure Al target and the second magnetron with a composed Al/Cu target. The amount of Al and Cu in the Al–Cu–O film was controlled by the length of pulse at the Al/Cu target. The Al–Cu–O films with ≤16 at.% Cu were investigated in detail. The addition of Cu in Al₂O₃ film strongly influences its structure and mechanical properties. It is shown that (1) the structure of Al–Cu–O film gradually varies with increasing Cu content from γ-Al₂O₃ at 0 at.% Cu through (Al_8−2x,Cu_3x)O₁₂ nanocrystalline solid solution to CuAl₂O₄ spinel structure, (2) the Al–Cu–O films with ≥3 at.% Cu exhibit (i) relatively high hardness H increasing from ∼15 GPa to ∼20 GPa, (ii) enhanced elastic recovery W_e increasing from ∼67% to ∼76% with increasing Cu content from ∼5 to ∼16 at.% Cu and (iii) low values of Young's modulus E* satisfying the ratio H/E* > 0.1 at ≥5 at.% Cu, and (3) highly elastic Al–Cu–O films with H/E* > 0.1 exhibit enhanced resistance to cracking during indentation under high load.     

The first high-resolution infrared study of diazirinone, N2CO: Analysis of the Fermi-coupled ν1 and 2ν5 bands

The first validated detection of the elusive diazirinone molecule (N₂CO) in the gas phase was performed using high-resolution infrared spectra recorded in the 1810–2100 cm⁻¹ region. The ν₁ and 2ν₅ bands were identified at 2043.8 and 1863.3 cm⁻¹ close to the ab initio prediction [X.Q. Zeng, H. Beckers, H. Willner, J.F. Stanton, Angew. Chem. Int. Ed. 50 (2011) 1720–1723]. For these two bands, the individual lines exhibit a (2:1) intensity alternation, confirming a three membered ring structure (C_2V symmetry) for N₂CO. The major output of the ν₁ and 2ν₅ bands analysis is the first experimental determination of the ground-state rotational constants of cyclic N₂CO. The observed intensity pattern of the ν₁ and 2ν₅ bands is in agreement with the existence of a strong Fermi resonance coupling the 1¹ and 5² energy levels.     

Complexation of bis‐crown stilbene with alkali and alkaline‐earth metal cations. Ultrafast excited state dynamics of the stilbene‐viologen analogue charge transfer complex

The complex formation of bis(18‐crown‐6)stilbene ( 1 ) and its supramolecular donor‐acceptor complex with N,N′‐bis(ammonioethyl) 1,2‐di(4‐pyridyl)ethylene derivative ( 2 ) with alkali and alkaline‐earth metal perchlorates has been studied using absorption, steady‐state fluorescence, and femtosecond transient absorption spectroscopy. The formation of 1 ?Mⁿ⁺ and 1 ?(Mⁿ⁺)₂ complexes in acetonitrile was demonstrated. The weak long‐wavelength charge‐transfer absorption band of 1 · 2 completely vanishes upon complexation with metal cations because of disruption of the pseudocyclic structure. The spectroscopic and luminescence parameters, stability constants, and 2‐stage dissociation constants were calculated. The initial stage of a recoordination process was found in the excited complexes 1 ?M⁺ and 1 ?(M⁺)₂ (M = Li, Na). The pronounced fluorescence quenching of 1 · 2 is explained by very fast back electron transfer (τ_et = 0.397 ps). The structure of complex 1 · 2 was studied by X‐ray diffraction; stacked ( 1 · 2 )_m polymer in which the components were connected by hydrogen bonding and stacking was found in the crystal. These compounds can be considered as novel optical molecular sensors for alkali and alkaline‐earth metal cations.     

The infrared spectrum of the Ar-CO complex Comprehensive analysis including van der Waals stretching and bending states

The infrared spectrum of the weakly-bound Ar-CO van der Waals complex in the 2150 cm^-1 region of the CO stretch has been studied using a continuous supersonic slit jet expansion coupled with a tunable laser spectrometer, and also with a cooled (57 K) long-path cell coupled with a Fourier transform spectrometer. Seven new subbands were observed, and previously observed bands were observed in greater detail. Four substates were thus identified for the first time, including the excited van der Waals stretching state, v ₃ = 1, and the excited bend, v ₂ = 1, within the ground CO stretching state, v _CO = 0. A comprehensive simultaneous analysis was made of all the existing infrared and microwave data on the complex for levels with K < 5, in order to obtain an accurate and self-consistent set of substate origins, rotational parameters, and centrifugal distortion parameters. A strong Coriolis interaction between K = 1 of the excited bend and K = 0 of the excited stretch was analysed in detail.     

A Mössbauer study of some new compounds with the Fe-Me [Me=Mo,Ni, Cu,Co, Hg,Zn, Cd,Mn, Fe] bond

The reaction of trans-(Co)₃Fe(PPh₂Py)₂ with MeXn gave nine new compounds of trans-(CO)₃Fe(PPh₂Py)₂MeXn (MeXn=Co(SCN)₂, Ni(SCN)₂, Fe(SCN)₃, Cd(SCN)₂, Mn(SCN)₂, Zn(SCN)₂, Mo(CO)₃, Hg(SCN)₂ and CuBr). The compositions of the compounds were determined through elemental analysis. The structural determination was made by IR, FD-MS and³¹P-NMR. Mössbauer spectra were taken at 78 K. The solid-state structure of the complex has been determined by a single-crystal X-ray diffraction study. The crystal data for trans-(CO)₃Fe(Ph₂PPy)₂Hg(SCN)₂ are:a=16.369(5) Å,b=13.754(3) Å,c=17.749(2) Å,r=108.95(2)°, monoclinic space group P21/n,Z= 4. The determination of ESCA demonstrated the change in the Fe value. In the present paper, the effect of the ligands on Fe-metal bonds is discussed.     

Charge ordering in crystals of Pr1? x Sr x MnO3 ( x = 0.22, 0.24) ferromagnetic manganites

The structural and magnetic states of Pr_1−x Sr _x MnO₃ (x = 0.22, 0.24) manganite crystals were studied over a wide temperature range. Measurements of the magnetic susceptibility and electrical resistivity demonstrated that these manganites belong to the class of ferromagnetic semiconductors. Thermal neutron elastic scattering patterns revealed that, in the temperature range 4.2–350 K, the manganites have an orthorhombic structure (space group Pnma) with a well-pronounced cooperative Jahn-Teller effect. Major emphasis was placed on the nuclear magnetic superstructure with a wave vector q = (2π/2a, 0, 2π/2c). It was shown that this superstructure suggests 1/4-type charge ordering in the manganites under investigation. Original Russian Text ? S.F. Dubinin, S.G. Teploukhov, V.E. Arkhipov, V.D. Parkhomenko, é.A. Neĭfel’d, A.V. Korolev, N.A. Ugryumova, Ya.M. Mukovskiĭ, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 4, pp. 704–710.     

The Molecular Structure of Morpholine and the Morpholine–H2O Complex Determined by FT Microwave Spectroscopy

The rotational spectrum of the morpholine–H₂O complex was measured and assigned using a Balle–Flygare type FT microwave spectrometer. Rotational, quartic centrifugal distortion, and¹⁴N quadrupole coupling constants were determined, and a N … H–O hydrogen-bonded structure was found to be consistent with the derived molecular parameters. Additionally, the rotational spectrum of the¹³C and¹⁵N isotopomers of the morpholine monomer were measured in natural abundance to determine itsr₀structure and a partial heavy atomr_sstructure.