The permanent electric dipole moment of holmium monoxide, HoO

The high resolution molecular beam laser-induced fluorescence (LIF) spectrum of the (0, 0) band of the [17.6]7.5-X₁8.5 system of holmium monoxide, HoO, has been recorded field free and in the presence of a variable static electric field. The rotational constant, B₀, and magnetic hyperfine structure constant, h, for the v = 0 levels of the [17.6]7.5 and X₁8.5 states were obtained by assigning and fitting the field-free spectral features. The Stark shifts and splittings in the LIF spectra were analyzed to produce values for the magnitude of the permanent electric dipole moments, |μ|, of 3.96(6) and 4.80(5) D for [17.6]7.5, v = 0 and X₁8.5, v = 0, respectively.     

Molecular speciation of microparticles: application of pattern recognition techniques to laser microprobe mass spectrometric data

Attempts were made to enhance the ability of laser microprobe mass spectrometry (LAMMS) to identify molecular species in individual microparticles by applying pattern recognition methods. Principal component analysis (PCA) and canonical discriminant analysis were applied to LAMMS data for nickel-containing environmental particles. Detailed comparison of the two statistical methods demonstrated the utility of PCA. The successful application was highly dependent on the use of appropriate spectral normalization and feature extraction techniques prior to PCA. Although the test system involved only a small number of standard compounds, the LAMMS data were complicated by the effects of intra-particle heterogeneity common to environmental samples and by instrumental limitations. Pattern recognition techniques provided more accurate quantitative assignments of molecular species than were available by qualitative inspection of characteristic cluster ions or by simple spectral subtraction to compare particle data with a library of standard compounds. Results were substantiated by comparison with bulk analysis studies using wet chemical techniques.     

Uncovering Organizational Hierarchies

This paper adapts a procedure, canonical analysis of asymmetry,originally defined by Gower (1977) to the analysis of hierarchicalproperties in organizational structures. Its application is demonstratedusing two available data sets, Freeman and Freeman's (1980) data on computercommunication and Krackhardt's (1987) data on advice-giving and getting inan organization.     

Electronic states of the CeO molecule: Absorption,emission, and laser spectroscopy

The electronic spectrum of the CeO molecule is characterized by the existence of many 0-0 bands resulting from transitions between various Ω components of excited states and the 16 lower Ω states which arise from the lowest configuration… (4f)(6s). Classical studies of rotational structure of absorption and emission spectra have been extended, and argon-ion and tunable dye (coumarin 460, rhodamine 6G, rhodamine 101) lasers have been used to excite known transitions in bands which had previously been rotationally analyzed. The resulting fluorescence spectra have been used to establish the relative energies of the lower states. By tuning the lasers to excite analyzed transitions from different known electronic states it has been possible to determine the energies of 16 low-lying states, to assign quantum numbers to 14 with certainty, and to suggest assignments for the other 2. The resulting energy level diagram of lower states is discussed and shown to correlate well with the 4f6s configuration of the Ce²⁺ ion. From the energies of the low-lying states, those of the higher excited states are calculated and in some cases new values of vibrational and rotational constants are derived.     

Examination of two new low-lying electronic states of SiS observed in chemiluminescent flame spectra

Diatomic silicon sulfide molecules have been produced in the chemiluminescent reaction of silicon atoms with OCS. Spectra of the resulting flame consist mainly of two new band systems in the region 350–400 and 385–600 nm. These systems have been assigned as b ³Π_r-X ¹Σ⁺ and a ³Σ⁺-X ¹Σ⁺ on the basis of band structure, spin-orbit splitting, molecular constants, and comparison with chemiluminescent spectra of isovalent molecules. Vibrational assignments were made with the help of the isotope effect and vibrational constants were obtained. Rotational structure was observed in some a-X bands and a partial analysis yielded an approximate rotational constant, B 0.247 ± 0.007 cm⁻¹, for the a ³Σ⁺ state. Franck-Condon factors, calculated for the a-X system, are shown to fit the general trend of the intensity distribution. Irregularities in spin-orbit splitting and in relative intensities of the spin-orbit components of the b ³Π-X ¹Σ⁺ system were observed and an attempt is made to explain them in terms of interactions with neighboring states. Addition of active nitrogen to the flame was shown to greatly increase the intensity of the b-X system relative to the a-X system. Constants (in cm⁻¹) obtained for the new state are: a³σ⁺: T_e=24 582.1 ± 1.3, ω_e=503.8±1.0, ω_ex_e=1.86±0.21b³σ⁺: T_e=27 314.5 ± 2.2, ω_e=619.4±2.0, ω_ex_e=5.75±0.52b³σ⁺: T_e=27 407.9 ± 1.1, ω_e=524.3±1.2, ω_ex_e=3.97±0.28     

A high resolution visible spectrum of iridium monophosphide

Laser induced fluorescence spectra of iridium monophosphide, IrP, have been obtained at low and high resolution in the blue region of the visible spectrum. Two electronic transitions were observed with origins near 459.6 and 471.9 nm. Three vibronic bands in each of these transitions have been observed at high resolution allowing for full characterization of the states. A J-independent doubling of the rotational lines has been ascribed to nuclear electric quadrupole coupling in the ground state. Multireference configuration interaction (MRCI) calculations have been performed in order to confirm the nature of the ground state and aid in the assignment of the excited states. The two observed transitions have been assigned as the [21.7]¹Σ⁺-X¹Σ⁺ and the [21.2] ³Σ⁺-X¹Σ⁺ electronic systems based on comparison with the theoretical calculations. The v + 2 level of each of these electronic transitions was found to be heavily perturbed and a successful deperturbation analysis was performed allowing for a complete global fit of the data.     

Catalytic enantioselective Meerwein-Eschenmoser Claisen rearrangement: asymmetric synthesis of allyl oxindoles

The first catalytic, enantioselective Meerwein-Eschenmoser Claisen rearrangement has been achieved. Palladium(II) BINAP or phosphinooxazoline catalysts were employed to generate oxindole products with 100% conversion and up to 92% ee.     

beta-sheet hydrogen bonding patterns in cystine peptides

Cystine peptides have been shown to adopt conformations in organic solvents that mimic small beta-sheets. Relative hydrogen bond strengths, beta-strand aggregation, and the identity of individual hydrogen bond donors and acceptors have been identified through hydrogen/deuterium exchange.