29 research outputs found

    High resolution infrared spectroscopy of carbon dioxide clusters up to (CO 2) 13

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    Thirteen specific infrared bands in the 2350 cm -1 region are assigned to carbon dioxide clusters, (CO 2) N, with N = 6, 7, 9, 10, 11, 12 and 13. The spectra are observed in direct absorption using a tuneable infrared laser to probe a pulsed supersonic jet expansion of a dilute mixture of CO 2 in He carrier gas. Assignments are aided by cluster structure calculations made using two reliable CO 2 intermolecular potential functions. For (CO 2) 6, two highly symmetric isomers are observed, one with S 6 symmetry (probably the more stable form), and the other with S 4 symmetry. (CO 2) 13 is also symmetric (S 6), but the remaining clusters are asymmetric tops with no symmetry elements. The observed rotational constants tend to be slightly ( 482%) smaller than those from the predicted structures. The bands have increasing vibrational blueshifts with increasing cluster size, similar to those predicted by the resonant dipole-dipole interaction model but significantly larger in magnitude. \ua9 2011 American Institute of Physics.Peer reviewed: YesNRC publication: Ye

    Fundamental and torsional combination bands of two isomers of the OCS-CO2 complex in the CO2 \u3bd3 region

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    Spectra of two isomers of the weakly bound complex OCS-CO2 are observed in the region of the CO2 \u3bd3 fundamental vibration ( 3c2349 cm-1), using an infrared tunable diode laser to probe a pulsed supersonic slit-jet expansion. Two bands are measured and analyzed for each isomer, the fundamental asymmetric stretch of the CO 2 component and a combination band involving this fundamental plus the intermolecular out-of-plane torsional mode. For one isomer, the corresponding torsional combination band is also detected in the OCS \u3bd1 stretching region ( 3c2060 cm-1). The resulting torsional frequencies are found to be 18.8 and 15.9 cm-1 for isomers a and b of OCS-CO2, respectively. This may be the first time that such a combination band is observed for a higher-energy isomer of a weakly bound complex. \ua9 2013 American Chemical Society.Peer reviewed: YesNRC publication: Ye

    NEW INFRARED SPECTRA OF THE NITROUS OXIDE TRIMER

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    Author Institution: Department of Physics and Astronomy, University of Calgary; Calgary, AB T2N 1N4, CANADA; Steacie Institute for Molecular Sciences, National Research; Council of Canada, Ottawa, ON K1A 0R6, CANADAInfrared spectra of N2_{2}O trimers are studied using a tunable diode laser to probe a pulsed supersonic slit-jet expansion. A previous observation by R.E. Miller and L. Pedersen [J. Chem. Phys. \textbf{108}, 436 (1998)] in the N2_{2}O \nub{1}+\nub{3} combination band region (~3480 cm−1^{-1}) showed the trimer structure to be noncyclic, with three inequivalent N2_{2}O monomer units which could be thought of as an N2_{2}O dimer (slipped antiparallel configuration) plus a third monomer unit lying above the dimer plane. The present observations cover the N2_{2}O fundamental band regions \nub{3} (~1280 cm−1^{-1}) and \nub{1} (~2230 cm−1^{-1}). In the \nub{3} region, two trimer bands are assigned with vibrational shifts and other characteristics similar to those in the \nub{1}+\nub{3} region, but in the \nub{1} region all three possible trimer bands are observed. Relationships among the various bands such as rotational intensity patterns, vibrational shifts, and the properties of the related N2_{2}O dimer, generally support the conclusions of Miller and Pedersen. Three trimer bands are also observed for the fully 15\ ^{15}N-substituted species in the \nub{1} region, and these results should aid in detection of the as-yet-unobserved pure rotational microwave spectrum of the trimer. Finally, three combination bands involving the intermolecular van der Waals modes at 2253.7, 2255.5, and 2269.4 cm−1^{-1} have been measured. The analyses of these bands and the identification of the nature of the intermolecular modes involved are currently underway

    INFRARED SPECTRA OF (CO2_{2})2_{2}-OCS COMPLEX: INFRARED OBSERVATION OF TWO DISTINCT BARREL-SHAPED ISOMERS

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    Author Institution: Department of Physics and Astronomy, University of Calgary, Calgary, AB T2N; 1N4, Canada; Steacie Institute for Molecular Sciences, National Research Council of; Canada, Ottawa, ON K1A 0R6, CanadaSpectra of (CO2_{2})2_{2}-OCS complex in the region of the OCS ν1\nu _{1} fundamental ( ∼\sim 2062 cm−1^{-1}) are observed using a tunable diode laser to probe a pulsed supersonic slit jet expansion. A previous microwave study of the complex by Peebles and Kuczkowskia gave a distorted triangular cylinder. The geometerical disposition of the three dimer faces of this trimer are quite similar to the slipped CO2_{2} dimer, the lowest energy form of OCS-CO2_{2} (isomer a), also observed and analyzed in the microwave region, and the higher energy form of OCS-CO2_{2} (isomer b), first observed by our group in the infrared region. Here we report the observation and analysis of two infrared bands, corresponding to two distinct isomers of the (CO2_{2})2_{2}-OCS complex. A band around 2058.8 cm−1^{-1} was assigned to isomer I, which is the same as that studied previously by microwave spectroscopy. A second band around 2051.7 cm−1^{-1} was assigned to a higher energy isomer of the complex, isomer II, has not been observed previously, but expected on the basis of \textit{ab initio} calculations. Approximate structural parameters for this new isomer were obtained by means of isotopic substitution. In contrast to isomer I, the geometerical disposition of the faces containing OCS and CO2_{2} in isomer II are similar to isomer b of the OCS-CO2_{2} complex
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