High-Resolution Infrared Spectroscopy of van der Waals Clusters of Nitrous Oxide, Carbon Dioxide and OCS-R Complexes
Date
2013-05-10
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Abstract
Weakly-bound van der Waals complexes containing OCS and various hydrocarbons, and clusters of N2O, and CO2 are studied by means of their rotationally-resolved infrared spectra. Clusters are generated in a pulsed supersonic jet expansion with two slit-shaped nozzles and probed with a tuneable diode laser.
Study of OCS-R complexes (R indicates certain hydrocarbons with chain or ring structures) commenced with the study of OCS-acetylene complex in the region of nu1 stretching fundamental of OCS (~2060 cm-1). Two bands are observed and assigned to near-parallel and T-shaped isomers of OCS-acetylene. In addition to the normal species, the deuterated isotopic form is also studied.
Simple looking bands characteristic of a T-shaped structure are observed for complexes formed between OCS and ethylene, allene, propyne, dimethylacetylene, benzene, and cyclo-octatetraene. All the bands are observed to be red-shifted from the OCS monomer nu1 frequency.
Infrared bands in the CO2 nu3 region (~2350 cm-1) are assigned to carbon dioxide clusters, (CO2)N, with N=6, 7, 9, 10, 11, 12, and 13. Assignments are aided by cluster calculations using two reliable CO2 intermolecular potential functions. These are the largest molecular clusters studied by infrared spectroscopy with rotational resolution. Two highly symmetric isomers with S6 and S4 symmetries are observed for (CO2)6. (CO2)13 is also symmetric with S6 symmetry, but all the remaining clusters are asymmetric tops. The bands have increasing blue-shifts with increasing cluster size, similar to predictions of resonant dipole-dipole model but considerably larger in magnitude.
N2O tetramer is studied in the region of N2O nu1 fundamental (~2220 cm-1). The previously observed oblate isomer of (N2O)4 is studied with considerably higher resolution. Isotopic substitution has confirmed a structure with D2d symmetry for this isomer. In addition to the oblate isomer, a new prolate isomer of (N2O)4 with S4 symmetry is observed.
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Physics--Molecular
Citation
Norooz Oliaee, J. (2013). High-Resolution Infrared Spectroscopy of van der Waals Clusters of Nitrous Oxide, Carbon Dioxide and OCS-R Complexes (Doctoral thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca. doi:10.11575/PRISM/26361