HIGH RESOLUTION LASER SPECTROSCOPY OF IRIDIUM MONOFLUORIDE AND

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 MF 11 Adam et al presented high resolution analysis of 2 electronic transitions of Ir. F (Laura Downie, Aaron Granger)

Analyzed and fitted A – X Transitions Problem fitting 3 -0 band. Heavily perturbed 3 A i 0 -1 0 -0 3 X i 1 -0 2 -0 3 -0 0 -0 ' =2 3 2 ' =3 3 3 ' = 4 3 4 '' = 2 3 2 '' = 3 3 3 '' = 4 3 4 1 -0

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

Ir. F 0 -0 1 -0 3 A Φ 4 3 -X Φ Rotational Structure 4

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

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 1/2 off diagonal matrix element was proportional to [J(J+1)] 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’(Ω=5)| J-L+ 3 |X Φ > = a 4 ½ [J(J+1)-Ω(Ω+1)] where a = <ν(A’)|B|ν(X)><A’(Ω=5)| L+ 3 | Φ > 4

-1 (cm ) Deperturbed Parameters for the A′ Ω=5 States of Ir. F State 3 A Φ 4 v = 3 Parameter T B 7 10 D T(J=0) A′ Ω = 5 T B 6 10 D T(J=0) a rms ~0. 002 -1 cm 191 Ir. F 3 A Φ 4 v=3 and Ir. F 17018. 2470(10) 17017. 5547(08) 193 0. 251910(23) 0. 251757(6) 2. 80(26) 2. 09(7) 17014. 2164 17013. 5266 17019. 1293(12) 17018. 7928(12) 0. 275066(43) 0274646(24) 1. 37(48) 3. 66(12) 17012. 2527 17011. 9267 0. 16401(5) 0. 16771(4)

Energy plots for the States A Ω=4 v=3 and A’ Ω=5 v’ of Ir. F

Ir. Cl (Samantha Foran) Low Resolution Spectrum Ir. C

Dispersed fluorescence of Ir. Cl Laser exciting 1 -0 band 2214 V” 0 1 405 2 0 408 401 3 Relative Wavenumber 386 -1 (cm ) 1

Dispersed fluorescence of Ir. F Laser exciting A-X 2 -0 Band 2210 V” 0 -1 cm (Ir Spin-orbit? ? ? ) 2 4 5 1 0 1 2 6 3 7 4

High Resolution Spectrum of Ir. Cl 1 -0 Band 13

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

Comparisons State Co. F 3Φ Rh. F 3Π Ir. F 3Φ Bo -1 (cm ) ro(Å) e ״ -1 (cm ) i 0. 388527 1. 738 663 i 0. 27245 1. 964 575 0. 283584 1. 851 650 i Bo Co. Cl 3Φ Rh. Cl 3Π Ir. Cl 3Φ -1 (cm ) ro(Å) e ״ -1 (cm ) i 0. 1793156 2. 070 433. 79 i 0. 124762 2. 274 348 0. 12248 2. 106 413. 22 i 15

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