The cyclic CO2 trimer: observation of a parallel band and determination of an intermolecular out-of-plane torsional frequency

A new parallel (DeltaK=0) band of the cyclic CO(2) trimer is observed at 2364 cm(-1). The trimers are generated in a pulsed supersonic expansion from a slit-jet nozzle and probed with a tunable infrared diode laser. The band is assigned as a combination of an intramolecular CO(2) monomer nu(3) stretch and an intermolecular out-of-plane torsion, giving a torsional frequency of 12-13 cm(-1). The band is surprisingly strong and completely unperturbed, providing a rare and near perfect example for a parallel band of a symmetric top molecule with C(3h) symmetry and zero nuclear spins.     

Measurement and revised analysis of the torsional combination band of the nonpolar N2O dimer at 2249 cm(-1)

The high-resolution infrared spectrum of the weakly-bound dimer (N(2)O)(2) is studied using a rapid-scan tunable-diode laser spectrometer to probe a pulsed supersonic jet expansion. An observed band with c-type rotational structure is assigned as a combination of the intramolecular N(2)O nu(1) stretching vibration and the intermolecular out-of-plane dimer torsional vibration, with a vibrational origin at 2249.360 cm(-1). The resulting torsional frequency for the nonpolar N(2)O dimer is about 21.5 cm(-1). The present rotational analysis is completely different from that reported previously for the same band [Hecker et al., Phys. Chem. Chem. Phys., 2003, 5, 2333], which gave a band origin some 1.53 cm(-1) lower.     

Dinuclear copper complexes of pyridylphenylphosphine ligands: Characterization of a mixed-valence Cu/Cu dimer

Homo bi-copper complexes [Cu₂{PhP(2-py)₂}₂(NO₃)₃] (1) and [Cu₂{P(2-py)₃}₂Cl₂] (2), were synthesized from the reaction of Cu(NO₃)₂·3H₂O and CuCl₂·2H₂O with their corresponding 2-pyridylphosphine ligands. Compound 1 has a mixed valence Cu(I)-Cu(II) core with electron acceptor phosphine atoms and two NO₃⁻ anions coordinated in a monodentate fashion to Cu(I), giving it a distorted tetrahedral geometry. The environment of Cu(II) in 1 is composed of four nitrogen atoms from pyridyl and another NO₃⁻ anion in a square pyramidal geometry. This complex shows luminescence and a low energy absorption band at 969 nm corresponding to intermetallic electron transfer between the copper centers. Complex 2 was prepared from the treatment of copper(II) chloride with tris(2-pyridyl)phosphine, producing a binuclear copper complex which possesses a crystallographic inversion center. The copper geometry in this complex is distorted tetrahedral with coordination of one Cl⁻, two nitrogens from one bridging tris(2-pyridyl)phosphine ligand and one P atom from the other bridging tris(2-pyridyl)phosphine ligand, in a similar way observed in related complexes. The products have been characterized by spectroscopic methods and also by the single-crystal X-ray diffraction method.     

A new laser dye with potential for high stability and a broad band of lasing action: Perylene-3,4,9,10-tetracarboxylic acid-bis-N,N′(2′,6′ xylidyl)diimide

We have obtained high gain lasing action from a dye in the calss of perylene-tetracarboxylic acid diimides. These dyes have been used in the past as microcrystalline pigments and more recently as molecularly dissolved fluors having both an orange absorption color and orange fluorescence. In dimethylformamide this dye absorbs with a main maximum at 527 nm, well coupled to the exciting radiation from a frequency-doubled YAG exciting laser. The dye lases primarily in the 0′→ 1″ satellite of the fluorescence band from 566–585 nm, with intermittent output pulses to 605 nm. While this dye overlaps the lasing bands of the rhodamine dyes, we believe that it may be considerably more stable than even Rhodamine 6G, the most stable of that class.     

Nitrous oxide dimer: observation of a new polar isomer

Spectra of the nitrous oxide dimer (N2O)2 are studied in the region of the N2O nu1 fundamental band around 2230 cm-1 using a rapid-scan tunable diode laser spectrometer to probe a pulsed supersonic jet expansion. The previously known band of the centrosymmetric nonpolar dimer is analyzed in improved detail, and a new band is observed and assigned to a polar isomer of (N2O)2. This polar form of the dimer has a slipped parallel structure, rather similar to the slipped antiparallel structure of the nonpolar form but with a slightly larger intermolecular distance. The accurate rotational parameters determined here should enable a microwave observation of the polar N2O dimer. The need for a modern ab initio investigation of the N2O-N2O intermolecular potential energy surface is emphasized.