AB INITIO STUDY OF ELECTRONIC SPECTRUM OF THE $CF_{2}$ RADICAL,
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Date
1993
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Publisher
Ohio State University
Abstract
The equilibrium geometries, excitation energies, force constants and vibrational frequencies for several low-lying electronic states $X ^{1}A_{1}, ^{1}B_{1}, 5A_{2}, ^{1}A_{2}, ^{1}A_{2}, ^{3}B_{2}$, and $^{1}B_{2}$, of the $CF_{2}$ radical have been calculated at the MRSDCI level with a triple-zeta plus double polarization $(TZ+2P)$ basis set. Our calculations imply that the $X ^{1}A_{1} \rightarrow ^{3}B_{2}$ and $X ^{1}A_{1} \rightarrow ^{1}B_{2}$ transitions may correspond to new band systems near 1500 and 1350 {\AA} in the absorption spectrum of $CF_{2}$ of ref 1. Our calculated excitation energies and vibrational frequencies for the ground state $X ^{1}A_{1}$ and excited states $^{3}B_{1} ^{1}B_{1}. ^{3}B_{2}$ and $^{1}B_{2}$ of $CF_{2}$ are in good agreement with available experimental data. Electronic transition dipole moments, oscillator strengths for the $^{1}B_{1} \to X ^{1}A_{1}$ and $^{1}B_{2} \to X ^{1}A_{1}$ transitions, radiative lifetimes for the 1B1 and 1B2 states are calculated based on the MRSDCI wavefunctions, predicting results in reasonable agreement with available experment.
Description
$^{1.}$C. W.Mathews, Can. J. Phys. 45,2355 (1967).
Author Institution: Department of Chemistry, East China Institute of Technology
Author Institution: Department of Chemistry, East China Institute of Technology