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The role of neutral hydrogen in setting the abundances of molecular species in the Milky Way's diffuse interstellar medium. I. Observational constraints from ALMA and NOEMA

We have complemented existing observations of HI absorption with new observations of HCO$^+$, C$_2$H, HCN, and HNC absorption from the Atacama Large Millimeter/submillimeter Array (ALMA) and the Northern Extended Millimeter Array (NOEMA) in the direction of 20 background radio continuum sources with $4^\circ \leq |b| \leq 81^\circ$ to constrain the atomic gas conditions that are suitable for the formation of diffuse molecular gas. We find that these molecular species form along sightlines where $A_V \gtrsim 0.25$, consistent with the threshold for the HI-to-H$_2$ transition at solar metallicity. Moreover, we find that molecular gas is associated only with structures that have an HI optical depth $> 0.1$, a spin temperature $< 80$ K, and a turbulent Mach number $\gtrsim 2$. We also identify a broad, faint component to the HCO$^+$ absorption in a majority of sightlines. Compared to the velocities where strong, narrow HCO$^+$ absorption is observed, the HI at these velocities has a lower cold neutral medium (CNM) fraction and negligible CO emission. The relative column densities and linewidths of the different molecular species observed here are similar to those observed in previous experiments over a range of Galactic latitudes, suggesting that gas in the solar neighborhood and gas in the Galactic plane are chemically similar. For a select sample of previously-observed sightlines, we show that the absorption line profiles of HCO$^+$, HCN, HNC, and C$_2$H are stable over periods of $\sim 3$ years and $\sim 25$ years, likely indicating that molecular gas structures in these directions are at least $\gtrsim 100$ AU in size