Organometallic quinonoid linkers: a versatile tether for the design of panchromatic ruthenium(II) heteroleptic complexes

The synthesis, X-ray structure determination, and photophysical investigation of a novel series of heteroleptic ruthenium(II) polypyridine complexes with organometallic linkers are reported. The displayed panchromatic absorption features are assigned by means of time-dependent density functional theory studies.     

The rotational spectrum of 13C2HD in the ground and excited bending states

The pure rotational spectrum of ¹³C₂HD was recorded in the range 100–700 GHz. Lines belonging to the ground vibrational state were observed from J^″ = 1 to J^″ = 11. Several absorption lines were also detected in the bending states v₄ = 1 (Π), v₅ = 1 (Π), v₄ = 2 (Σ⁺ and Δ), v₅ = 2 (Σ⁺ and Δ), v₄ = v₅ = 1 (Σ^?, Σ⁺ and Δ), v₄ = 3 (Π and Φ) and v₅ = 3 (Π and Φ). The transition frequencies measured in this work were fitted together with all the infrared lines available in the literature. The global fit allowed a very accurate determination of the vibrational, rotational and ?-type interaction parameters for the bending states of this molecule.     

Fortran Formac Products of Non Numerical Matrices

In some dynamical problems one may need to perform repeatedly non numerical calculations on algebraic expressions. In such a case one can use the FORMAC system which allows to carry out algebraic calculations on a digital computer. Since we have afforded this problem in one particular case, we wish to illustrate this application of FORMAC in order to bring to the attention of chemical physicists the existence of such computational technique.     

Stable particles in anisotropic spin-1 chains

Motivated by field-theoretic predictions we investigate the stable excitations that exist in two characteristic gapped phases of a spin-1 model with Ising-like and single-ion anisotropies. The sine-Gordon theory indicates a region close to the phase boundary where a stable breather exists besides the stable particles, that form the Haldane triplet at the Heisenberg isotropic point. The numerical data, obtained by means of the Density Matrix Renormalization Group, confirm this picture in the so-called large-D phase for which we give also a quantitative analysis of the bound states using standard perturbation theory. However, the situation turns out to be considerably more intricate in the Haldane phase where, to the best of our data, we do not observe stable breathers contrarily to what could be expected from the sine-Gordon model, but rather only the three modes predicted by a novel anisotropic extension of the Non-Linear Sigma Model studied here by means of a saddle-point approximation.     

Microwave spectrum of the32S17O radical. Magnetic hyperfine structure and quadrupole coupling constants

Summary The millimetre wave spectrum of the³²S¹⁷O free radical has been observed and analysed. The fine- and hyperfine-structure parameters have been determined. Ther ^s andr ^m structures have been also determined.

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Riassunto è stato osservato ed analizzato lo spettro millimetrico del radicale libero³²S¹⁷O. Sono stati determinati i parametri di struttura fine ed iperfine e le strutturer ^s er ^m.

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Резюме Наблюдался д проведен анализ спектра миллиметровых волн свободного радикала³²З¹⁷О. Определены параметры тонкой и сверхтонкой структуры. Также определены структурыr ^s иr ^m.

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To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.

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The supporting organizations are the CNR and the M.P.I.     

Surface Dynamics of A Vanadyl Pyrophosphate Catalyst for n‐Butane Oxidation to Maleic Anhydride: An In Situ Raman and Reactivity Study of the Effect of the P/V Atomic Ratio

This work focused on investigating the effect of the P/V atomic ratio in vanadyl pyrophosphate, catalyst for n‐butane oxidation to maleic anhydride, on the nature of the catalytically active phase. Structural transformations occurring on the catalyst surface were investigated by means of in situ Raman spectroscopy in a non‐reactive atmosphere, as well as by means of steady‐state and non‐steady‐state reactivity tests, in response to changes in the reaction temperature. It was found that the nature of the catalyst surface is affected by the P/V atomic ratio even in the case of small changes in this parameter. With the catalyst having P/V equal to the stoichiometric value, a surface layer made of α_I‐VOPO₄ developed in the temperature interval 340–400 °C in the presence of air; this catalyst gave a very low selectivity to maleic anhydride in the intermediate T range (340–400 °C). However, at 400–440 °C δ‐VOPO₄ overlayers formed; at these conditions, the catalyst was moderately active but selective to maleic anhydride. With the catalyst containing a slight excess of P, the ratio offering the optimal catalytic performance, δ‐VOPO₄ was the prevailing species over the entire temperature range investigated (340–440 °C). Analogies and differences between the two samples were also confirmed by reactivity tests carried out after in situ removal and reintegration of P. These facts explain why the industrial catalyst for n‐butane oxidation holds a slight excess of P; they also explain discrepancies registered in the literature about the nature of the active layer in vanadyl pyrophosphate.     

Millimeter- and submillimeter-wave spectroscopy of HBS and DBS in vibrationally excited states

Normal and deuterated isotopic variants of thioborine have been produced in the gas phase by a high temperature reaction between crystalline boron and hydrogen sulfide. Millimeter- and submillimeter-wave rotational spectra have been recorded in the frequency range from 75 to 730 GHz for vibrational ground and excited states of the H^10/11B³²S and D^10/11B³²S isotopic species. The spectra of all the excited states which lie below 1500 cm⁻¹, that are 01¹0, 00⁰1, 02⁰0, and 02²0, have been observed and analyzed for each of the four isotopologues investigated. High-order Fermi resonance parameters were found important to analyze properly the spectra of the 00⁰1 and 02⁰0 interacting states. The improved rotational data in conjunction with earlier infrared spectroscopy results have been employed to calculate more precise anharmonic force constants and equilibrium bond lengths.     

Millimeter-Wave Spectroscopy of Sulfur Dichloride

The rotational spectra of (32)S(35)Cl(2), (32)S(35)Cl(37)Cl, (32)S(37)Cl(2), and (34)S(35)Cl(2) in their ground vibrational states, as well as those of (32)S(35)Cl(2) and (32)S(35)Cl(37)Cl in their nu(2) and 2nu(2) excited states, have been studied in selected frequency regions between 100 and 370 GHz. Transitions involving a large range of quantum numbers have been observed, so that precise rotational and quartic centrifugal distortion constants could be determined for each of the spectra investigated. The complete set of sextic distortion constants was also obtained for the most abundant isotopomer in its ground vibrational state. The newly determined rotational constants of (34)S(35)Cl(2) and (32)S(37)Cl(2) allowed us to calculate the complete r(s) structure of sulfur dichloride using both single- and double-isotopic substitution methods. The quadratic force field has been refined using a larger set of quartic distortion constants and inertial defects. Copyright 2000 Academic Press.     

Millimeter-Wave Spectroscopy of ClBS: An Improved Evaluation of the Equilibrium Structure of Chlorothioborine

The rotational spectrum of the unstable ClBS molecule has been investigated in the millimeter-wave region, from 80 to 195 GHz. A high-temperature reaction between crystalline boron and disulfur dichloride vapor was used to produce the molecule in a flow pyrolysis system. Eight different isotopic species were studied measuring lines in the ground and excited vibrational states 01¹0 (ClBS bend), 10⁰0 (ClB stretch), 02⁰0, 02²0, and 00⁰1 (BS stretch). The analysis of the spectra has been performed taking simultaneously into account both the Fermi resonance between the 10⁰0 and 02⁰0 states, and l-type resonance effects in the v₂=2 vibrational state. This procedure allowed us to calculate directly deperturbed rotational constants, from which the equilibrium rotational constant of seven isotopic variants could be accurately determined yielding a much improved evaluation of the equilibrium structure of chlorothioborine: r_e(ClB)=1.6806±0.0001 Å and r_e(BS)=1.6049±0.0001 Å. The equilibrium structures of ClBS and of the related molecules HBS, FBS, HCP, FCP, and ClCP have been also theo-retically evaluated by high-level CCSD(T) calculations performed using cc-pVTZ, cc-pVQZ, and cc-pV5Z basis sets. The different trends respectively observed for the BS and CP bond lengths in the XBS and XCP triatomic molecules are discussed.     

The steady-state toroidal magnetized plasma «thorello» for basic plasma physics research

Summary Thorello is a steady-state toroidal magnetized plasma suitable for basic plasma physics experiments. The discharge is produced in hydrogen by hot-filament electron emission and acceleration by a bias. Electron temperature and density have been evaluated by electrostatic probes. Excitation and detection by an interferometric method of electrostatic ion cyclotron waves (ESICW) have permitted the evaluation of ion temperature.

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Riassunto Thorello è un plasma magnetizzato stazionario particolarmente adatto per esperimenti di fisica del plasma di base. La scarica è prodotta in idrogeno per mezzo di elettroni emessi da un filamento caldo ed accelerati da una differenza di potenziale. La temperatura e la densità elettronica sono state valutate per mezzo di sonde elettrostatiche. La temperatura ionica è stata ricavata mediante un metodo interferometrico basato sull’eccitazione e la rilevazione di onde elettrostatiche ioniche di ciclotrone (ESICW).