Leah C. O'Brien and Kaitlin Womack Department of Chemistry

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Presentation transcript:

Intracavity Laser Absorption Spectroscopy of Platinum Fluoride in the Near-Infrared Leah C. O'Brien and Kaitlin Womack Department of Chemistry Southern Illinois University, Edwardsville, IL 62026-1652 James J. O'Brien, Meredith Reddick, and Rebecca Steinberg University of Missouri, St Louis, MO 63121-4499

MO Diagram: PtF isoelectronic with NiF -4 -2 -6 -8 -10 -12 -14 -16 Pt F PtF 5d 6s 2p σ δ π

Previous Work – Theoretical Relativistic calculations on the low-lying 2Π, 2Δ, and 2Σ states: Liu and Franke, J. Comp. Chem. 23 (2002) 564-575. Without Spin-Orbit With Spin-Orbit Te (eV) re (Å) 2Σ 0.000 1.921 2Π 0.252 1.913 2Δ 0.462 1.942 Te (eV) re (Å) X 2Π3/2 0.000 1.873 Ω=1/2 0.106 1.894 2Δ5/2 0.167 1.915

Previous Work – Experimental Using intracavity laser absorption spectroscopy and a hollow cathode source, our lab recorded PtF spectra at 11940 and 12496 cm-1 Analyzed and assigned as the (0,0) and (1,0) bands of a 2Π3/2 – X 2Π3/2 transition 1st spectroscopic observation Kimberly G. Handler, Rachel A. Harris, Leah C. O’Brien, James J. O’Brien, “Intracavity laser absorption spectroscopy of platinum fluoride, PtF,” JMS 265 (2011) 39–46 Microwave spectrum of PtF in preliminary stages (Tanimoto et al.)

ILS Schematic Diagram

Intracavity Laser Spectroscopy Use ILS to search for more transitions of PtF Platinum-lined hollow cathode Trace SF6 as oxidant in ~1.6 Torr Argon 0.35 to 0.60 Amp for discharge current Ti:Sapphire laser Calibrate with I2 spectra/atlas

12523 cm-1 Band of PtF

12523 cm-1 Band of PtF A strong bandhead was observed at 12523 cm-1 Several branches were observed Very small splittings observed in the R-branch Probably (0,0) band [12.5] 2Σ+ State in cm-1 T0,0 12513.2005 B0 .2575887 D0 .510 x 10-6 γ0 1.256 Consistent with 2Σ – X 2Π3/2 transition Fit data with standard 2Σ+ and 2Π3/2 polynomials

13079 cm-1 Band of PtF

13079 cm-1 Band of PtF A strong bandhead was observed at 13079 cm-1 Several branches were observed 0.2 cm-1 splittings observed in the R-branch Assigned as the (1,0) band ΔG½′ = 551.53 cm-1 [12.5] 2Σ+ State v=1 in cm-1 T1 13064.7332 B1 .2570087 D1 .490 x 10-6 γ1 1.222 Based on “Fit 2”

Conclusions New spectroscopic observations of PtF Bands at 12423 and 13079 cm-1 are analyzed and assigned as the (0,0) and (1,0) bands of a new [12.5] 2Σ+ – X 2Π3/2 transition of PtF Preliminary molecular constants are determined for the excited states Future work: Look for transitions involving the low-lyng =1/2 states

Acknowledgements Funding from NSF (JJOB and LCOB) St. Louis area STARS Program Rebecca Steinberg and Meredith Redick worked on the (0,0) band SIUE undergraduate Kaitlin Womack Thank you for your attention!