Precision spectra of $A\, ^2Σ^+,v'=0 \leftarrow X\, ^2Π_{3/2},v''=0,J''=3/2$ transitions in $^{16}$OH and $^{16}$OD

Abstract

We report absolute optical frequencies of electronic transitions from the $X\, ^2Π_{3/2},v''=0,J''=3/2$ rovibronic ground state to the 12 lowest levels of the $A\, ^2Σ^+,v'=0$ vibronic state in $^{16}$OH, as well as to the 16 lowest levels of the same vibronic state in $^{16}$OD. The absolute frequencies of these transitions have been determined with a relative uncertainty of a few parts in $10^{11}$, representing a $\sim$1000-fold improvement over previous measurements. To reach this level of precision, an optical frequency comb has been used to transfer the stability of a narrow-linewidth I$_2$-stabilized reference laser onto the 308-nm spectroscopy laser. The comb is also used to compare the optical frequency of the spectroscopy laser to an atomic clock reference, providing absolute accuracy. Measurements have been carried out on OH/OD molecules in a highly-collimated molecular beam, reducing possible pressure shifts and minimizing Doppler broadening. Systematic shifts due to retroreflection quality, the Zeeman effect, and the ac Stark effect have been considered during the analysis of the measured spectra; particularly in the case of the OD isotopologue, these effects can result in shifts of the fitted line positions of as much as 300 kHz. The transition frequencies extracted in the analysis were also used to determine spectroscopic constants for the $A\, ^2Σ^+,v'=0$ vibronic state. The constants fitted in this work differ significantly from those reported in previous works that measured the $A - X$ transitions, resulting in typical deviations of the predicted optical transition frequencies of $\sim$150 MHz, but they generally agree quite well with the constants determined using hyperfine-resolved measurements of splittings within the $A$ state.