Raman scattering enables unforeseen uses for the laser guide-star system of the Very Large Telescope. Here, we present the observation of one up-link sodium laser beam acquired with the ESPRESSO spectrograph at a resolution $lambda/Deltalambda sim 140000$. In 900s on-source, we detect the pure rotational Raman lines of $^{16}$O$_2$, $^{14}$N$_2$, and $^{14}$N$^{15}$N (tentatively) up to rotational quantum numbers $J$ of 27, 24, and 9, respectively. We detect the $^{16}$O$_2$ fine-structure lines induced by the interaction of the electronic spin textbf{S} and end-over-end rotational angular momentum textbf{N} in the electronic ground state of this molecule up to $N=9$. The same spectrum also reveals the $ u_{1leftarrow0}$ rotational-vibrational Q-branch for $^{16}$O$_2$ and $^{14}$N$_2$. These observations demonstrate the potential of using laser guide-star systems as accurate calibration sources for characterizing new astronomical spectrographs.
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