Optical-Optical Double Resonance Spectroscopy of the Quasi-Linear S₂ State of CHF and CDF. I. Spectroscopic Analysis


In this work, we report on our full results of the spectroscopic analysis of the quasi-linear S2 state of the prototypical halocarbene, CHF, and its deuterated isotopomer CDF using optical-optical double resonance spectroscopy through the S1 state. A total of 51 S2 state vibrational levels with angular momenta in the range 0-3 were observed for CHF, and 76 levels for CDF. Progressions involving all three fundamental vibrations were observed, and rotational constants were determined for each of these levels by measuring spectra through different intermediate J levels of the S 1 state. Our experimental results are in excellent agreement with the predictions of vibrational calculations using the discrete variable representation method. The variational vibrational calculations were performed with an analytic potential energy surface fit to ab initio data by the method of interpolating moving least squares. The ab initio data are Davidson-corrected multi-reference configuration interaction calculations based on a state-averaged multiconfigurational self-consistent field reference incorporating a generalized dynamic weighting scheme.



Keywords and Phrases

Ab initio; Discrete variable representation; Fundamental vibrations; Interpolating moving least squares; Multiconfigurational self-consistent fields; Multireference configuration; Optical-optical double resonance spectroscopy; Quasi-linear; Rotational constants; Vibrational calculations; Vibrational levels; Weighting scheme; Calculations; Deuterium; Least squares approximations; Quantum chemistry; Table lookup; Vibration analysis; Spectroscopic analysis

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