Laser-induced fluorescence (LIF) measurements are made on the <i>C</i><sup>2</sup>Σ<sup>+</sup>-<i>X</i><sup>2</sup>Π<sub>r</sub> (λ = 314 nm) transition of CD, which is produced by a microwave-excited Ar/CD<sub>4</sub> process plasma. The experiment is realized by using a frequency-doubled cw ring dye laser as the tunable light source. Due to the small bandwidth (≈3 MHz) of the exciting UV laser, the exact line positions of spin-doubled rotational lines in the <i>P</i>-branch (<i>N</i>″ = 2 to 5 and <i>N</i>″ = 8 to 13) of the first vibrational band (<i>v′ = v″</i> = 0) could be determined. The resolution is limited only by Doppler broadening, which amounts in our plasma (<i>T</i> = 450 K) to about 4 GHz. With these new values of line positions, a modified spin-splitting constant of γ = 0.051 ± 0.006 cm<sup>−1</sup> is calculated.
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