1. 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
James J. O'Brien, Meredith Reddick, and Rebecca Steinberg
University of Missouri, St Louis, MO

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

3. Previous Work – Theoretical
Relativistic calculations on the low-lying 2Π, 2Δ, and 2Σ states: Liu and Franke, J. Comp. Chem. 23 (2002)
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

4. Previous Work – Experimental
Using intracavity laser absorption spectroscopy and a hollow cathode source, our lab recorded PtF spectra at and 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.)

5. ILS Schematic Diagram

6. 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

7. 12523 cm-1 Band of PtF

8. 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 B0 D0
.510 x 10-6 γ0
1.256
Consistent with 2Σ – X 2Π3/2 transition
Fit data with standard 2Σ+ and 2Π3/2 polynomials

9. 13079 cm-1 Band of PtF

10. 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′ = cm-1
[12.5] 2Σ+ State
v=1
in cm-1 T1 B1 D1
.490 x 10-6 γ1
1.222
Based on “Fit 2”

11. Conclusions New spectroscopic observations of PtF
Bands at and 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

12. 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!