First detection and absolute transition frequencies in the (3–0) band of D2

Three electric quadrupole transitions in the second overtone band of D2 are newly measured by comb-referenced cavity ring down spectroscopy around 1.18 µm. These extremely weak transitions (line intensities smaller than 10−29 cm/molecule) are the first to be detected in the (3–0) band of D2. The spectra of the O(3), O(2), and Q(2) lines near 8321, 8446, and 8607 cm−1, respectively, are recorded at room temperature for pressure values ranging between 100 and 600 Torr. Accurate transition frequencies and line intensities of the three D2 transitions are determined from a line fitting procedure using beyond-Voigt profiles, including strong Dicke narrowing. Considering statistical fit errors and possible biases due to the interference with water lines (which are six orders of magnitude stronger than the studied D2 lines), total uncertainties on the frequencies extrapolated at zero pressure are estimated below 14 MHz (∼4.7 × 10−4 cm−1). The derived experimental frequencies and intensities are compared to ab initio values. An overall agreement is achieved, confirming the positional accuracy of the most advanced theoretical calculations.