TRANSITION MOMENT VARIATION FROM HIGHLY OVERLAPPED SPECTRA: XENON FLUORIDE $B(\frac{1}{2})-X(^{2}\Sigma^{+})$ AND $D(\frac{1}{2}) – X(^{2}\Sigma^{+})^{*}$
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Date
1979
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Ohio State University
Abstract
Photographic absorption spectra of a flash-photolysed mixture of Xe (750 Torr) and $F_{2}$ (50 Torr) show extended band structure for both B-X (294 - 355 nm) and D-X (239-265 nm) transitions of XeF. Despite extensive overlapping by hot bands, we determined the R-variation of both B-X and D-X transition moments using ``band-cluster analysis’’, in which both cold and hot bands within a given wavelength region are shown to have quite similar R-centroids. We find that the B-X moment is independent of R between 2.30 and 2.54 A; normalizing to the $measured^{1}$ radiative lifetime of $19.4 \pm 1$ nsec for $\nu ^{\prime} = o$ of XeF(B(1/2)), the transition moment is $2.70 \pm 0.22$ Debye in this range of R. Since B-X and D-X absorptions were recorded on the same exposure, the absolute D-X moment could be determined, and varies linearly from 2.255 Debye at 2.25 A to 2.413 Debye at $2.50 A (\pm 15%)$. The computed radiative lifetime of XeF (D(1/2), $\nu^{\prime}= $o) is $10.0 \pm 2$ nsec.
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$^{*}$Supported by DOE under LASL Contract EN-77-S-04-3902 $^{1}$ C.H. Fisher and R.E. Center, J. Chem. Phys. 69, 2011 (1978).
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