1hv spectrum corrected/shifted CF3Br agust,heima,....CF3Br/Sept10/PXP-291110ks/Br 1D-REMPImW-291110ks-011210ak.pxp agust,heima,....CF3Br/Sept10/PXP-291110ks/Br 1D-REMPImW-291110ks-021210ak.pxp agust,www,....cf3br/PPT-011210ak.ppt agust,heima,....CF3Br/Sept10/PXP-291110ks/Leiðrétt-291110ks-011210ak.pxp agust,heima,....CF3Br/Sept10/PXP-291110ks/Leiðrétt-291110ks-021210ak.pxp

Irel 2hv Br atomic lines (2+1)REMPI From “short scans” For spectra corrected for power As Icorr = Imeasured / P5 NB: “mW-power correction” Irel Digitized 1hv spectrum from S. Eden et al., CP, 322, 313 (2006) 2hv agust,heima,....CF3Br/Sept10/PXP-291110ks/Br 1D-REMPImW-291110ks-011210ak.pxp

1hv spectrum corrected/shifted Br atomic lines (2+1)REMPI From “short scans” For spectra corrected for power As Icorr = Imeasured / P5 NB: “mW-power correction” Irel Digitized 1hv spectrum from S. Eden et al., CP, 322, 313 (2006) 2hv agust,heima,....CF3Br/Sept10/PXP-291110ks/Br 1D-REMPImW-291110ks-021210ak.pxp

NB: We assume that the relative intensities of the Br atomic lines for the “short scans” and low step size (0.1 cm-1) are more reliable than those or the “long scans” and larger step size (0.2 cm-1)

Irel 2hv Digitized 1hv spectrum from S. Eden et al., CP, 322, 313 (2006) Irel Br atomic lines “short scans” “mW-power corrected” 0.1 cm-1 step size Br atomic lines “mJ-power corrected” 0.2 cm-1 step size 2hv agust,heima,....CF3Br/Sept10/PXP-291110ks/Br 1D-REMPImW-291110ks-011210ak.pxp

1hv spectrum corrected/shifted Digitized 1hv spectrum from S. Eden et al., CP, 322, 313 (2006) 1hv spectrum corrected/shifted Irel Br atomic lines “short scans” “mW-power corrected” 0.1 cm-1 step size Br atomic lines “mJ-power corrected” 0.2 cm-1 step size 2hv agust,heima,....CF3Br/Sept10/PXP-291110ks/Br 1D-REMPImW-291110ks-021210ak.pxp

Irel 2hv It is not clear from the spectra comparison below how to correct relative intensities of Br atomic lines recorded by “long scans” Band step size 0.2 cm-1, since there does not seem to be any systematic relationship in relative intensities when compared with the “short scan” spectra Irel Br atomic lines “mW-power corrected” 0.1 cm-1 step size Br atomic lines “mJ-power corrected” 0.2 cm-1 step size 2hv agust,heima,....CF3Br/Sept10/PXP-291110ks/Br 1D-REMPImW-291110ks-011210ak.pxp

The conclusion is that Br atomic lines in the high wavenumber range (> 80000cm-1) need to be rescanned by short scans and small step sizes (0.1 cm-1) in order to obtain more relyable picture of the relative intensities of The bands in that region. Based on the data presented in slide 2, abowe, for Br atomic lines recorded in the range 71000 – 80000 cm-1 (“short scans”, small step sizes) the largest signals are observed for the region of excitation to the [CF3Br+,2E]c ;5p Rydberg state whereas atomic lines corresponding to excitations to the region to the [CF3Br+,2E]c ; 5s Rydberg state are very weak. This suggests that the major channel For formation of Br is via excitation to the [CF3Br+,2E]c ;5p Rydberg state. This fits nicely with the results of the CF3+ formation analaysis: See: http://www3.hi.is/~agust/rannsoknir/rempi/cf3br/PPT-201110ak.ppt and below

Irel CF3+ 2hv Digitized 1hv spectrum from S. Eden et al., CP, 322, 313 (2006) CF3+ 2hv agust,heima,....CF3Br/Sept10/PXP-291110ks/Leiðrétt-291110ks-011210ak.pxp

1hv spectrum corrected/shifted Irel Digitized 1hv spectrum from S. Eden et al., CP, 322, 313 (2006) CF3+ 2hv agust,heima,....CF3Br/Sept10/PXP-291110ks/Leiðrétt-291110ks-021210ak.pxp