• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.189-194
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• 2002

Two-photon resonant third photon ionization of atomic bromine $(4p^5\;^2P_{3/2}\;and\;^2P_{1/2})$ has been studied using a photoelectron imaging spectroscopy in the wavelength region 250 - 278 nm. The technique has yielded simultaneously both relative branching ratios to the three levels of $Br^+(^3P_2,\;^3P_{0.1}\;and^1D_2)$ with $4p^4$ configuration and the angular distributions of outgoing photoelectrons. The product branching ratios reveal a strong propensity to populate particular levels in many cases. Several pathways have been documented for selective formation of $Br^+(^3P_2)$ and $Br^+(^3P_{0.1})$ ions. In general, the final ion level distributions are dominated by the preservation of the ion core configuration of a resonant excited state. Some deviations from this simple picture are discussed in terms of the configuration interaction of resonant states and the autoionization in the continuum. The photoelectron angular distributions are qualitatively similar for all transitions, with a positive $A_2$ anisotropy coefficient of 1.0-2.0 and negligible $A_4$ in most cases, which suggests that the angular distribution is mainly determined by the single-photon ionization process of a resonant excited state induced from the third photon absorption.

• Bulletin of the Korean Chemical Society
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• v.35 no.3
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• pp.815-820
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• 2014

We applied the two-color resonant two-photon ionization and mass-analyzed threshold ionization techniques to record the vibronic and cation spectra of 2,4-difluorophenol. As supported by our theoretical calculations, only the cis form of 2,4-difluorophenol involves in the two-photon photoexcitation and pulsed field ionization processes. The band origin of the $S_1{\leftarrow}S_0$ electronic transition of cis-2,4-difluorophenol appears at 35 647 ${\pm}2cm^{-1}$ and the adiabatic ionization energy is determined to be 70 $030{\pm}5cm^{-1}$, respectively. Most of the observed active vibrations in the electronically excited $S_1$ and cationic ground $D_0$ states mainly involve in-plane ring deformation vibrations. Comparing these data of cis-2,4-difluorophenol with those of phenol, cis-2-fluorophenol, and 4-fluorophenol, we found that there is an additivity rule associated with the energy shift resulting from the additional fluorine substitution.