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

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