The high-accuracy spectroscopy of H rovibrational transitions in the (2-0) band near 1.2 μm.

Accurate transition frequencies of six lines of the (2-0) vibrational band of H are reported near 1.2 μm, namely Q1-Q4, S0, and S1. These weak electric-quadrupole transitions were measured at room temperature by comb-referenced cavity ring-down spectroscopy. Accurate transition frequencies were determined by applying a multi-spectrum fit procedure with various profile models including speed-dependent collisional broadening and shifting phenomena. Although none of the considered profiles allows reproducing the shape of the strongest lines at the noise level, the zero-pressure line centers are found mostly independent of the used profile. The obtained values are the first H (2-0) transition frequencies referenced to an absolute frequency standard. As a result, a 1-accuracy better than 100 kHz was achieved for the Q1, S0, and S1 transition frequencies, improving by three orders of magnitude the accuracy of previous measurements. For the six measured transitions, the most recent calculated frequencies were found to be systematically underestimated by about 2.51 MHz, about twice their claimed uncertainties. The energy separation between = 2 and = 0 rotational levels of the vibrational ground state was derived from Q2 and S0 transition frequencies and found within the 110 kHz uncertainty of its theoretical value. The same level of agreement was achieved for the energy separation between the = 3 and = 1 rotational levels obtained by the difference of Q3 and S1 transition frequencies. The values of the intensity of the six transitions were validated within a few thousandths.