Microwave spectroscopic study of the SiF radical

The microwave spectrum of the SiF radical was observed in both ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ of the ground vibronic state. The SiF radical was produced by a dc discharge either in a $\text{SiF}{}_4\text{SiH}{}_4$ mixture or in a transient molecule SiF₂ generated by the reaction of SiF₄ with heated solid silicon. The latter gave twice as intense a spectrum. A least-squares fit to the observed spectrum showed the rotational constant and the centrifugal distortion constant to be 17 350.2752(63) and 0.03188(13) MHz, respectively, with three standard errors in parentheses applying to the last digits of the constants. The lambda-doubling parameter p₀ was found to be negative, ?87.67 MHz, indicating that the ²Σ⁺ excited state contributions dominate over those of ²Σ^?. All four hyperfine coupling constants a, b, c, and d were determined and were employed to discuss the unpaired-electron spin and orbital distributions in the SiF radical.