1. 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, CHAMPAIGN-URBANA, ILLINOIS

2. 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

3. 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)

4. 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)

5. 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)

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

7. 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

8. Molecular constants for 102RuF
State
T /cm-1
B / cm-1
D / 107 cm-1
a / 103 cm-1
X(4.5)
(67)
2.939(51)
1.9(18)
[13.1]3.5
(10)
(43)
9.4(16)
[18.2]5.5
(24)
(65)
2.473(48)
11.7(11)
[22.2]3.5
(42)
(14)
-3.43(19)
S”(3.5)
(86)
1.94(29)
S’(3.5)
(35)
(82)
8.81(18)
V”(4.5)
(89)
V’(5.5)
(17)
(96)

9. 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

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

11. 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)

12. 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)

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

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

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

16. 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

17. Any Questions?

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