Bending modes metrology in the 14-15 $\mu$m region

Frequency combs have triggered an impressive evolution of optical metrology across diverse regions of the electromagnetic spectrum, from the ultraviolet to the terahertz frequencies. An unexplored territory, however, remains in the region of vibrational bending modes, mostly due to the lack of single-mode lasers in the long-wavelength (LW) part of the mid-infrared (MIR) spectrum. We fill this gap through a purely MIR-based nonlinear laser source with tunability from 12.1 to 14.8 $\mu$m, optical power up to 110 $\mu$W, MHz-level linewidth and comb calibration. This enables the first example of bending modes metrology in this region, with the assessment of several CO$_2$-based frequency benchmarks with uncertainties down to 30 kHz, and the accurate study of the $\nu_{11}$ band of benzene, which is a significant testbed for the resolution of the spectrometer. These achievements pave the way for LW-MIR metrology, rotationally-resolved studies and astronomic observations of large molecules, such as aromatic hydrocarbons.