HIGH RESOLUTION LASER SPECTROSCOPY OF IRIDIUM MONOFLUORIDE AND IRIDIUM MONOCHLORIDE A.G. ADAM, L. E. DOWNIE, S. J. FORAN, A. D. GRANGER, D. FORTHOMME, C. LINTON AND D. W. TOKARYK Centre for Laser, Atomic and Molecular Sciences (CLAMS) Chemistry and Physics Departments University of New Brunswick, Fredericton NB Canada

Columbus 2008 Paper MF11 Adam et al presented high resolution analysis of 2 electronic transitions of IrF (Laura Downie, Aaron Granger)

Analyzed and fitted A – X Transitions  '' = 4  ' = 4  ' =3 A3iA3i X 3  i 3434 3434 3333 3333 3232 3232  ' =2  '' = 2  '' = Problem fitting 3-0 band. Heavily perturbed

Adam et al 2008 last slide Future Work Sort out the apparent hyperfine structure The 3-0 band of the red system is perturbed and there are extra lines Next targets for comparison are IrH and IrCl Next talk

IrF A 3 Φ 4 -X 3 Φ 4 Rotational Structure

Perturbation in the v=3 level of the A state R Branch head 3-0 Band 193 IrF 191 IrF J”

Analysis of perturbation in A state v=3 J assignments of main and extra lines in R Q P branches via ground state combination differences Intensities show that A and A’ states cross between J=7 and 8 Excellent simultaneous fit to the two bands obtained only when off diagonal matrix element was proportional to [J(J+1)] 1/2 Thus ΔΩ = ±1 ie Ω(A’) = 3 or 5 Fit showed that the R(4) line of the A-X transition was shifted by the interaction with the A’ state but the Q(4) and P(5) lines were unaffected. Thus A state J=5 is perturbed but J=4 is unperturbed Lowest level in A’ state is therefore J=5 and Ω=5 In the final fit, the off diagonal matrix element was = a [J(J+1)-Ω(Ω+1)] ½ where a =

StateParameter 191 IrF 193 IrF A 3 Φ 4 v = 3T (10) (08) B (23) (6) 10 7 D2.80(26)2.09(7) T(J=0) A′ Ω = 5T (12) (12) B (43) (24) 10 6 D1.37(48)3.66(12) T(J=0) a (5) (4) Deperturbed Parameters (cm -1 ) for the A 3 Φ 4 v=3 and A′ Ω=5 States of IrF rms ~0.002 cm -1

Energy plots for the States A Ω=4 v=3 and A’ Ω=5 v’ of IrF

Low Resolution Spectrum IrC IrCl (Samantha Foran)

Dispersed fluorescence of IrCl Laser exciting 1-0 band V” Relative Wavenumber (cm -1 )

Dispersed fluorescence of IrF Laser exciting A-X 2-0 Band V” cm -1 (Ir Spin-orbit???)

13 High Resolution Spectrum of IrCl 1-0 Band

14 IrCl 1-0 Band Head Region Wavenumber (cm -1 ) 193 Ir 35 Cl R Head 191 Ir 35 Cl R Head

15 Comparisons StateB o (cm -1 )r o (Å)  e ״ (cm -1 ) CoF 3Φi3Φi RhF 3Πi3Πi IrF 3Φi3Φi B o (cm -1 )r o (Å)  e ״ (cm -1 ) CoCl 3Φi3Φi RhCl 3Πi3Πi IrCl 3Φi3Φi

Conclusions Rotational analysis shows Co and Ir Halides have similar configurations giving 3 Φ i ground state. mixed (ndσ) 2 (nd δ) 3 (nd π) 3 + (ndσ)(nd δ) 3 (nd π) 3 ([n+1]sσ) where n = 3 for Co and n = 5 for Ir Different from Rh halides with 3 Π i ground state (4d δ) 4 (4d π) 3 (5sσ) v = 3 level of IrF A 3 Φ 4 state perturbed by an Ω = 5 state Dispersed fluorescence suggests ground state spin orbit splitting (3A) of ~2200cm -1 for both IrF and IrCl Unresolved hyperfine structure in both IrF and IrCl give broad lines at low J and doublets (quadrupole hyperfine) at higher J Need to study hyperfine structure to determine details of configuration. (Next talk!) Thanks to Joyce MacGregor