Accurately Measuring Molecular Rotational Spectra in Excited Vibrational Modes

Although gas phase rotational spectroscopy is a mature field for which millions of rotational spectral lines have been measured in hundreds of molecules with sub-MHz accuracy, it remains a challenge to measure these rotational spectra in excited vibrational modes with the same accuracy. Recently, it was demonstrated that virtually any rotational transition in excited vibrational modes of most molecules may be made to lase when pumped by a continuously tunable quantum cascade laser (QCL). Here, we demonstrate how an infrared QCL may be used to enhance absorption strength or induce lasing of terahertz rotational transitions in highly excited vibrational modes in order to measure their frequencies more accurately. To illustrate the concepts, we used a tunable QCL to excite v₃ R-branch transitions in N₂O and either enhanced absorption or induced lasing on 20 v₃ rotational transitions, whose frequencies between 299 and 772 GHz were then measured using either heterodyne or modulation spectroscopy. The spectra were fitted to obtain the rotational constants B₃ and D₃, which reproduce the measured spectra to within the experimental uncertainty of ± 5 kHz. We then show how this technique may be generalized by estimating the threshold power to make any rotational transition lase in any N₂O vibrational mode.