NEW ELECTRONIC STATES OF THE CHFCI RADICAL

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1994

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Ohio State University

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The electronic spectrum of the CHFCl radical was observed between 340-420 nm using one color, mass resolved, 2+1 resonance enhanced multiphoton ionization (REMPI) spectroscopy. The spectrum arises from two-photon resonance with the planar $\bar F (3p) (\lambda_{laser} = 406.7 nm, \nu_{\infty} = 49160(20) cm^{-1})$ and $J(3d)(\lambda_{laser} = 361.9 nm. \nu_{\infty} = 55250(20) cm^{-1})$ Rydberg states. A third laser photon ionized the radicals. Both states produced the same vibrational constants; $\nu_{2}$ (C-H deformation) $= 1280(30) cm^{-1}, \nu_{4}$ (C-Cl stretch) = 910(30) $cm^{-1}, \nu_{5}$ (CFCl scissors)$ = 440(30) cm^{-1},\nu_{6} (OPLA) = 980(30) cm^{-1})$. The REMPI spectrum exhibited $v_{0}^{\prime\prime} = 1-6$ hot bands of the CHFCI $(\tilde{X} ^{2}A)$ radical. Modeling of these hot bands with a double-well potential yields the inversion barrier, $B_{inv} = 1180 cm^{-1}$, and the angle between the F-C-Cl plane and the C-H bond, $\Phi_{e}=42^{\circ}$.

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Author Institution: Chemical Kinetics and Thermodynamics Division, Chemical Science and Technical Laboratory, National Institute of Standards and Technology

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