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Studying f-Electron Contributions in Thorium and Uranium Containing Molecules
The pure rotational spectra of several actinide-containing compounds have been improved upon and, in two cases, been recorded for the first time. The diatomic molecules HfS and ThS have been studied in their ground electronic states but high vibrationally excited states. The results have yielded very accurate locations of the minima of the potential energy curves. The asymmetric molecules OThS and UO2S have been prepared by laser ablation synthesis and their pure rotational spectra recorded for the first time. Precise information pertinent to the geometric and electronic structure of these molecules has been obtained and is compared with other, newly recorded and related species such as OCeS.
Pure rotational excitation in CO/plus/-Ar interactions by ion beam collision spectroscopy
Molecular rotational excitation during CO ion-Ar interactions by ion beam collision spectroscopy, observing energy loss spectra
Thermal bifurcation in the upper solar photosphere inferred from heterodyne spectroscopy of OH rotational lines
Low noise high spectral resolution observations of two pure rotation transitions of OH from the solar photosphere were obtained. The observations were obtained using the technique of optically null-balanced infrared heterodyne spectroscopy, and consist of center-to-limb line profiles of a v=1 and a v=0 transition near 12 microns. These lines should be formed in local thermodynamic equilibrium (LTE), and are diagnostics of the thermal structure of the upper photosphere. The v=0 R22 (24.5)e line strengthens at the solar limb, in contradiction to the predictions of current one dimensional photospheric models. Data for this line support a two dimensional model in which horizontal thermal fluctuations of order + or - 800K occur in the region Tau (sub 5000) approximately .001 to .01. This thermal bifurcation may be maintained by the presence of magnetic flux tubes, and may be related to the solar limb extensions observed in the 30 to 200 micron region.
Molecular structure determination: Equilibrium structure of pyrimidine (m-C 4 H 4 N 2 ) from rotational spectroscopy (reSE) and high-level ab initio calculation (re) agree within the uncertainty of experimental measurement
The pure rotational spectrum of pyrimidine (m-C 4 H 4 N 2 ), the meta-substituted dinitrogen analog of benzene, has been studied in the millimeter-wave region from 235 GHz to 360 GHz. The rotational spectrum of the ground vibrational state has been assigned and fit to yield accurate rotational and distortion constants. Over 1700 distinct transitions were identified for the normal isotopologue in its ground vibrational state and least-squares fit to a partial sextic S-reduced Hamiltonian. Transitions for all four singly substituted 13 C and 15 N isotopologues were observed at natural abundance and were likewise fit. Deuterium-enriched samples of pyrimidine were synthesized, giving access to all eleven possible deuterium-substituted isotopologues, ten of which were previously unreported. Experimental values of rotational constants and computed values of vibration–rotation interaction constants and electron-mass corrections were used to determine semi-experimental equilibrium structures (r e SE ) of pyrimidine. The r e SE structure obtained using coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] corrections shows exceptional agreement with the re structure computed at the CCSD(T)/cc-pCV5Z level (≤0.0002 Å in bond distance and ≤0.03° in bond angle). Of the various computational methods examined, CCSD(T)/cc-pCV5Z is the only method for which the computed value of each geometric parameter lies within the statistical experimental uncertainty (2σ) of the corresponding semi-experimental coordinate. The exceptionally high accuracy and precision of the structure determination is a consequence of the large number of isotopologues measured, the precision and extent of the experimental frequency measurements, and the sophisticated theoretical treatment of the effects of vibration–rotation coupling and electron mass. Taken together, these demanding experimental and computational studies establish the capabilities of modern structural analysis for a prototypical monocyclic aromatic compound.
Processing Raman Spectra of High-Pressure Hydrogen Flames
The Raman Code automates the analysis of laser-Raman-spectroscopy data for diagnosis of combustion at high pressure. On the basis of the theory of molecular spectroscopy, the software calculates the rovibrational and pure rotational Raman spectra of H2, O2, N2, and H2O in hydrogen/air flames at given temperatures and pressures. Given a set of Raman spectral data from measurements on a given flame and results from the aforementioned calculations, the software calculates the thermodynamic temperature and number densities of the aforementioned species. The software accounts for collisional spectral-line-broadening effects at pressures up to 60 bar (6 MPa). The line-broadening effects increase with pressure and thereby complicate the analysis. The software also corrects for spectral interference ("cross-talk") among the various chemical species. In the absence of such correction, the cross-talk is a significant source of error in temperatures and number densities. This is the first known comprehensive computer code that, when used in conjunction with a spectral calibration database, can process Raman-scattering spectral data from high-pressure hydrogen/air flames to obtain temperatures accurate to within 10 K and chemical-species number densities accurate to within 2 percent.
Sub-millimeter Spectroscopy of Astrophysically Important Molecules and Ions: Metal Hydrides, Halides, and Cyanides
With the advent of SOFIA, Herschel, and SAFIR, new wavelength regions will become routinely accessible for astronomical spectroscopy, particularly at submm frequencies (0.5-1.1 THz). Molecular emission dominates the spectra of dense interstellar gas at these wavelengths. Because heterodyne detectors are major instruments of these missions, accurate knowledge of transition frequencies is crucial for their success. The Ziurys spectroscopy laboratory has been focusing on the measurement of the pure rotational transitions of astrophysically important molecules in the sub-mm regime. Of particular interest have been metal hydride species and their ions, as well as metal halides and cyanides. A new avenue of study has included metal bearing molecular ions.
Thermal bifurcation in the upper photosphere inferred from heterodyne spectroscopy of OH rotational lines
Low-noise (S/N greater than 100), high spectral resolution observations of two pure rotation transitions of OH from the solar photosphere are used to make inferences concerning the thermal structure and inhomogeneity of the upper photosphere. It is found that the v = O R22(24.5)e line strengthens at the solar limb, in contradiction to the predictions of current one-dimensional photospheric models. The results for this line support a two-dimensional model in which horizontal thermal fluctuations in the upper photosphere are of the order plus or minus 800 K. This thermal bifurcation may be maintained by the presence of magnetic flux tubes and may be related to the solar limb extensions observed in the 30-200-micron region.
Spectroscopy of Chlorosyl Fluoride, FClO
FClO has been proposed as an intermediate in reactions involving ClF, Cl2O, and ClF3O, and it has been suggested as a molecule of atmospheric interest. It has been prepared in situ by the hydrolysis of ClF3. The pure rotational spectrum of FClO has been studied by conventional millimeter wave techniques and by microwave Fourier transform spectroscopy. Selected transitions were searched for using predictions based on an analysis of the nu(sub 1) band. FClO is an asymmetric prolate top, kappa = -0.8950 for F(35)ClO, with a rather small dipole component of 0.093 (4) D along the a-axis and a larger one of 1.93 (5) D along the b-axis. Transitions with 0 <= J <= 54 and 0 <= K(sub a) <= 18 were observed. Cl hyperfine splitting was generally observable throughout the spectrum with F-19 spin-rotation splitting observable as well in the microwave region. Structural parameters, harmonic force constants, and nuclear magnetic shielding parameters were derived and will be compared with data of related molecules, such as ClF3, ClF, FClO2, and FClO3. High resolution infrared spectra were taken in the regions of the FCl stretching mode and bending mode around 600 and 310/cm, respectively. A preliminary analysis indicates that the FCl stretch, near 596.86/cm for F(35)ClO, is in resonance with the dark overtone of delta near 617/cm. A brief progress report will be given.
The millimeter and submillimeter rotational spectrum of the MgCN radical (X (sup 2) Sigma(+))
The pure rotational spectrum of the MgCN radical has been recorded in the laboratory using millimeter/submillimeter direct absorption spectroscopy. Twenty-seven rotational transitions of the species were observed in the range 101-376 GHz and indicate that the molecule is linear with a (sup 2)Sigma(+) ground electronic state, as predicted by theory. Spin rotation interactions were resolved in the spectra, but no hyperfine splittings were observed, which would originate with the nitrogen nuclear spin. The rotational and fine-structure constants were determined for this radical from a nonlinear least-squares fit to the data using a (sup 2)Sigma Hamiltonian. MgCN is of astrophysical interest because it is the metastable isomer of MgNC, which recently has been detected toward IRC +10216
The millimeter-wave spectrum of the CaF radical (X(sup 2)Sigma(+))
The pure rotational spectrum of the CaF radical has been measured in the laboratory using millimeter/sub-mm direct absorption spectroscopy. Fourteen rotational transitions have been detected originating in the v = 0 mode of the species. Rotational lines of the vibrationally excited v = 1, 2, and 3 states have also been observed. Spin-rotation splittings, as well as hyperfine interactions arising from the nuclear spin of the fluorine atom, were resolved in the CaF spectra. Rotational, fine-structure, and in some cases, hyperfine parameters were determined for the various vibrational modes of the molecule from a nonlinear least-squares fit to the data, using a (sup 2)Sigma Hamiltonian, and are in agreement with past measurements. The newly measured rest frequencies for CaF, which are accurate to at least + or - 100 kHz, will enable astronomical searches to be conducted for the molecule in interstellar and circumstellar gas. Given the recent detection of AlF in IRC + 10216, metal fluoride species may be more abundant than previously thought.
Infrared absorption by OH containing compounds
The spectroscopy of the species H2O, H2O2, and HO2 are discussed. Their vibration rotation transitions are emphasized, but the pure rotational transitions in the vibrational ground state of H2O are also considered since they contribute to opacity in the middle infrared region.
Laboratory detection and millimeter spectrum of the MgCCH radical
The pure rotational spectrum of the magnesium monoacetylide radical, MgCCH, has been recorded in the laboratory using millimeter/sub-mm direct absorption spectroscopy. These measurements constitute the first time this molecule has been observed in the laboratory by any spectroscopic method. Seventeen rotational transitions were observed in the frequency range 210-370 GHz for MgCCH, which appears to be a linear molecule with a (sup 2)Sigma ground electronic state. Rotational and fine structure constants were determined for this radical from a nonlinear least squares fit to the data. The rotational rest frequencies measured here will enable astronomical observations to be carried out for MgCCH towards IRC +10216, where the magnesium compounds MgCN and MgNC, as well as many acetylide species, are present.
Molecular spectroscopy from the Kuiper Airborne Observatory
Interstellar and circumstellar molecules are investigated through medium-resolution infrared spectrosocpy of the vibration-rotation and pure rotational transitions. A primary goal was the construction and improvement of instrumentation for the near and middle infrared regions, wavelengths between 2 and 10 microns. The main instrument was a cooled grating spectrometer with an interchangeable detector focal plane which could be used on the Kuiper Airborne Observatory (KAO) for airborne observations, and also at ground-based facilities. Interstellar shock waves were investigated by H2 emission from the Orion Nebula, W51, and the proto-planetary nebulae CRL 2688 and CRL 618. The observations determined the physical conditions in shocked molecular gas near these objects. From these it was possible to characterize the energetic history of mass loss from both pre- and post-main sequence stars in the regions.
The millimeter/submillimeter rotational spectrum of CaCCH(X(sup 2)Sigma(+))
The pure rotational spectrum of the CaCCH radical (X(sup 2) Sigma(+)) has been measured in the laboratory using millimeter/submillimeter direct absorption spectroscopy. The species was created in a d.c. discharge by the reaction of calcium vapor and acetylene. Twenty-two rotational transitions of this molecule were recorded in the frequency range 230-380 GHz to an accuracy of +/- 150 kHz. Spin-rotation splittings, but no proton hyperfine structure, were observed for CaCCH. The data were analyzed using a (sup 2) Sigma Hamiltonian, and rotational and fine structure constants were determined. These measurements have resulted in accurate rest frequencies for CaCCH to be used for astronomical searches. A calcium-bearing molecule has yet to be observed in interstellar or circumstellar gas.
Millimeter and submillimeter rest frequencies for the MgF radical
The pure rotational spectrum of the MgF radical in its ground X(sup 2) Sigma(+) electronic state has been observed in the laboratory using millimeter/submillimeter direct absorption spectroscopy. Rotational transitions arising from the v = 0, 1, 2, and 3 vibrational modes of the main magnesium isotopic species, (24)MgF, have been recorded, as well as those arising from the v = 0 state of the Mg-25 and Mg-26 isotopomers. Rotational and fine-structure constants have been determined for these molecules, as well as hyperfine parameters for both the F-19 (I = 1/2) and Mg-25 (I = 5/2) nuclei. The rest frequencies presented here for MgF have an estimated accuracy of +/- 200 kHz, and will enable astronomical searches to be carried out for this fluoride radical. Magnesium fluoride may be present in the late-type carbon star IRC +10216, where AlF appears to be abundant.
Unsupported and carbon-supported silver catalysts for oxygen reduction reaction in alkaline media
Quick and easy Ag catalysts preparation via wet chemical synthesis method using only reducing agent (pure-Ag); reducing agent and citric acid as the capping agent (Ag-CA); and carbon support (KetjenBlack 600J), capping agent, and the reducing agent (Ag/C) is demonstrated. The Ag-based electrocatalysts are characterized by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) with energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of Ag catalysts for O 2 reduction reaction (ORR) in 1 M KOH is evaluated using the rotating (ring)-disc electrode method. SEM and HAADF-STEM results show that the unsupported pure-Ag and Ag-CA catalysts consist mainly of big agglomerates, and Ag/C has the smallest agglomerates and some sub-3 nm Ag nanoparticles. The XPS results reveal that Ag in all the catalysts is in the metallic form (Ag 0 ). Despite consisting of big agglomerates, the Ag-CA catalyst exhibits similar ORR electrocatalytic activity to that of Ag/C. Ag-CA (unsupported) shows the lowest hydrogen peroxide yield. These results are of great importance for the development of Ag-based catalysts that can be prepared in a fast, simple and easily up scalable fashion, for anion exchange membrane fuel cells.
First identification of pure rotation lines of NH in the infrared solar spectrum
Pure rotation lines of NH of the v = 0 level and v = 1 level are detected in high-resolution solar spectra obtained from the Atmospheric Trace Molecule Spectroscopy (ATMOS) experimental observations. It is pointed out that the identification of the lines is favored by the typical appearance of the triplet lines of nearly equal intensities. The observed equivalent widths of these triplet lines are compared with predicted intensities, and it is observed that these widths are systematically larger than the predicted values. It is noted that because these very faint lines are observed in a region where the signal is very low, a systematic error in the measurements of the equivalent widths cannot be ruled out; therefore, the disagreement between the observed and predicted intensities is not considered to be real.