Accurate deuterium spectroscopy and comparison with ab initio calculations

We present accurate measurements of the quadrupole S(3) and S(4) transitions of the D22-0 band. Self-perturbed spectra were collected in a wide pressure range with a cavity ring-down spectrometer linked to an optical frequency comb. The results of ab initio quantum scattering calculations were incorporated into the line-shape analysis which was performed using the Hartmann-Tran profile. This approach allowed us to mitigate the collisional systematics and to reach a 900-kHz accuracy of the transition frequencies, which represents a 30-fold improvement compared to previously available data. We also compare our findings with newly calculated transition frequencies that include relativistic and quantum electrodynamics corrections up to α7. The differences between theoretical and experimental values for the transition frequencies are 2.2 MHz and 3.3 MHz for the S(3) and S(4) transitions, respectively.