LASER-INDUCED FLUORESCENCE SPECTROSCOPY OF TWO RUTHENIUM-BEARING MOLECULES: RuF AND RuCl Hanif Zarringhalam,Department of Physics Allan G. Adam, Department of Chemistry Colan Linton, Dennis W. Tokaryk , Department of Physics University of New Brunswick International Symposium on Molecular Spectroscopy 72ND MEETING - JUNE 19-23, 2017 - CHAMPAIGN-URBANA, ILLINOIS

Previous work on RuF Ab initio calca. for RuFX4i; re=2.05 Å (B=0.251 cm-1) aPer E. Siegbahn, Theor. Chim. Acta (1993) 86, 219 Calculations [18.2]5.5 540 nm X44.5 Experiment

Low Resolution Spectra of RuF Observed by our group Precursor:SF6 (high resolution) Steimle’s group Steimle’s group (low res. only) Intensity (arb.) Wavelength (nm)

The Dispersed Florescence of RuF SO: ground-state spin-orbit component ES: low-lying excited state SO ES SO [22.1]3.5 state ES Intensity (arb.) [18.2]5.5 state [13,1]3.5 state Wavenumber (cm-1)

Three transitions in RuF Ω-values are determined by analysis of the first R and P lines in each spectrum. P(4.5) R(4.5) Ω = 3.5 R(4.5) P(6.5) Intensity (arb.) Ω = 5.5 P(4.5) R(4.5) Ω = 3.5 GS Ω = 4.5 Wavenumber (cm-1)

Hyperfine Interactions IRu =0,IF =1/2 101RuF,99RuF IRu=5/2,IF=1/2 (messy!) 102RuF 104RuF 100RuF 96RuF

The [18.2]5.5- transition of RuF We see two weak bands beside the strong one 0,0 band Ω’=5.5, Ω”=4.5 [19.2]4.5 v=1 [18.8]5.5 Vibration:1,1 band Ω’=5.5, Ω”=4.5 [18.2]5.5 Spin orbit Ω’=4.5, Ω”=3.5 v=1 [0.5]4.5

Molecular constants for 102RuF State T /cm-1 B / cm-1 D / 107 cm-1 a / 103 cm-1 X(4.5) 0.2866213(67) 2.939(51) 1.9(18) [13.1]3.5 13146.2588(10) 0.280586(43) 9.4(16) [18.2]5.5 18254.87345(24) 0.2881513(65) 2.473(48) 11.7(11) [22.2]3.5 22157.23135(42) 0.2822593(14) -3.43(19) S”(3.5) 0.2866738(86) 1.94(29) S’(3.5) 18237.63131(35) 0.2885004(82) 8.81(18) V”(4.5) 0.284232(89) V’(5.5) 18310.9254(17) 0.285987(96)

Summary: RuF [22.1]3.5 987 [19.2]4.5 v=1 [18.8]5.5 617 [18.2]5.5 [13.1]3.5 2002 X42.5 [2.0]2.5 988 From DF X43.5 [1.0]3.5 v=1 [0.6]4.5 560 X44.5

RuCl Low res survey Precursor: BCl3 (CCl4 only made RuC!) Intensity (arb.) Wavelength (nm)

High Resolution Spectrum of RuCl Intensity (arb.) P(8.5) 102Ru35Cl P(7.5) 102Ru35Cl P(6.5) 102Ru35Cl P(7.5) 102Ru37Cl P(8.5) 102Ru37Cl Wavenumber (cm-1)

Examples of DFs from RuCl Ground state ωe HfCl : 378 cm-1 FeCl: 405 cm-1 Intensity (arb.) Excited state : 260 cm-1 Wavenumber (cm-1)

Molecular constants for 102Ru35Cl State T / cm-1 B / cm-1 D / 107 cm-1 X(4.5) 0.12729079(970) 0.813(123) [17.5]4.5 17553.18494(20) 0.12498857(912) 0.700(108) [19.6]5.5 19666.83019(28) 0.12763115(594) 0.5352(215)

Summary of RuCl [19.6]5.5 [17.5] 4.5 [14.4] [13.8] (future work!) v=1 355 cm-1 260 cm-1 Low lying exited state X44.5

Work in progress Taking high resolution rotationally resolved spectra of infrared bands of RuCl . Extend the DF analysis of RuCl.

Acknowledgments Funding Supervisors Group members Dr.Dennis Tokaryk Dr.Allan Adam Dr.Colan Linton Joyce MacGregor Nick Caron Ben Nadeau Jacob Dore UNB NSERC Group members

Any Questions?

Previous experimental work on RuF aTimothy C.Steimle, J.Chem.Phys. 124,024309 (2006).