THE ELECTRONIC SPECTRUM OF THE $CCl_{3}$ RADICAL

Author Institution: Chemical Kinetics Division, Center for Chemical Technology National Institute of Standards and Technology; Chemical Kinetics Division, Center for Chemical Technology; Department of Chemistry, University of Minnesota at Duluth; Department of Environmental Chemistry and Biology, Johns Hopkins University School of Hygiene and Public HealthThe electronic spectrum of $C^{35}Cl_{3}$ radicals was observed between 336-440 ni using mass resolved resonance enhanced multiphoton ionization (REMPI) spectroscopy. This spectrum arose from two-photon resonances with planar Rydberg states. A third laser photon ionized the radicals. One Rydberg series of quantum defect $\delta= 0.545$ is comprised of the $\bar{E} 2_{E^{\prime}}$ (3p) state $(\nu_{0-0}=47170, w_{1}(a^{\prime}_{1}$ sym scr) = 544(6), $\omega^{\prime}_{2}(a_{2}^{\prime\prime}$ OPLA) = 509(21), spin-orbit splitting = $33(5) cm^{-1}$) and the $\tilde{K} ^{2}_{E^{\prime}} (4p)$ state $(\nu_{0-0}= 56236, \omega_{2}^{\prime}= 526(16) cm^{1})$. A second Rydberg series of $\delta =0,50$ is comprised of the $\bar{F} (3d) (\nu_{0-0})=51218 cm^{-1}, \omega_{2}^{\prime}=520(17) cm^{-1}$ and $\bar{M} (4d) (\nu_{0-0}= 57733 cm^{-1}, \omega_{2}^{\prime}= 542(16) cm^{1})$ states. A fit of the Rydberg formuls to these series found the adiabatic ionization potential of the $CCl_{3}$ radical to be $1P_{n}=B.109(5) eV$. The $\bar{J} ^{2}A_{2}^{\prime}(4s)$ Rydberg state $(\nu_{0-0}= 53471, \omega_{2}^{\prime}= 530(20) cm^{1})$ was also observed. The REMPI spectrum exhibited the $v_{2}^{\prime\prime}=1-4$ vibrational hot bands of the $\tilde{X} ^{2}A_{1} (C_{3v})$ radical. Modeling of these hot bands derived the inversion barrier, $B_{i n v} = 460 \pm 40 cm^{-1}