Theory vs. experiment for molecular clusters: Spectra of OCS trimers and tetramers

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DOIResolve DOI: http://doi.org/10.1063/1.4914323
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TypeArticle
Journal titleJournal of Chemical Physics
ISSN0021-9606
Volume142
Issue10
Article number104309
SubjectIsomers; Monomers; Organic polymers; Broad-band spectrum; Cluster calculations; Free structures; Infrared bands; Infrared spectrum; Molecular clusters; Pair potential; Oligomers
AbstractAll singly substituted 13C, 18O, and 34S isotopomers of the previously known OCS trimer are observed in natural abundance in a broad-band spectrum measured with a chirped-pulse Fourier transform microwave spectrometer. The complete substitution structure thus obtained critically tests (and confirms) the common assumption that monomers tend to retain their free structure in a weakly bound cluster. A new OCS trimer isomer is also observed, and its structure is determined to be barrel-shaped but with the monomers all approximately aligned, in contrast to the original trimer which is barrel-shaped with two monomers aligned and one anti-aligned. An OCS tetramer spectrum is assigned for the first time, and the tetramer structure resembles an original trimer with an OCS monomer added at the end with two sulfur atoms. Infrared spectra observed in the region of the OCS ν1 fundamental (≈2060 cm-1) are assigned to the same OCS tetramer, and another infrared band is tentatively assigned to a different tetramer isomer. The experimental results are compared and contrasted with theoretical predictions from the literature and from new cluster calculations which use an accurate OCS pair potential and assume pairwise additivity.
Publication date
PublisherAIP Publishing
LanguageEnglish
AffiliationNational Research Council Canada; Security and Disruptive Technologies
Peer reviewedYes
NPARC number21275751
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Record identifier0ff2eaa4-f2df-444b-a76a-c071c81d7b4b
Record created2015-07-14
Record modified2017-03-23
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