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Presentation
Mass-Independent Dunham Analysis of the Known Electronic States of PtS
International Symposium on Molecular Spectroscopy (2019)
  • Jack C. Harms, University of Missouri-St. Louis
  • Leah C. O'Brien, Southern Illinois University Edwardsville
  • James O'Brien, University of Missouri-St. Louis
Abstract
Several new vibrational bands of the [15.9] B Ω=0+-X 3Σ − (Ω=0+) and [12.5] Ω=0+-X 3Σ − (Ω=0+) transitions of PtS have been recorded at high resolution using Intracavity Laser Spectroscopy (ILS). These new bands have been rotationally analyzed and incorporated into a comprehensive PtS data set that was fit to a mass-independent Dunham expression using PGOPHER. The comprehensive data set included all of the reported spectroscopic data for PtS, including: 32 FTMW transitions (estimated accuracy: 1 kHz) [Cooke and Gerry, J. Chem. Phys., 121, 3486 (2004)], 9 MODR transitions (25 kHz) [Li et al., J. Mol. Spec., 170, 310 (1995)], 51 mm- and sub-mm transitions (25-50 kHz) [Okabayashi et al., J. Mol. Spec., 248, 7 (2012)], 469 MB-LIF transitions (0.003 cm−1 ) [Li et al.], and 4651 ILS transitions (0.005 cm−1 ) [Handler et al., J. Mol. Spec., 263, 78 (2010) and from this work]. Deviations from the Dunham model were observed due to both the breakdown of the Born-Oppenheimer approximation and field-shift effects resulting from differences in nuclear charge density between Pt-isotopes. The observed field-shift effects extended to isotope-dependent shifts in electronic excitation energy, which have been reported previously only for PbS (and for PtF and PtCl in recent work by our group). The results of the analysis and a discussion of the deviations from the Dunham model will be presented.
Keywords
  • Metal containing
Publication Date
2019
DOI
10.15278/isms.2019.WJ01
Citation Information
Jack C. Harms, Leah C. O'Brien and James O'Brien. "Mass-Independent Dunham Analysis of the Known Electronic States of PtS" International Symposium on Molecular Spectroscopy (2019)
Available at: http://works.bepress.com/james-obrien/25/