2021ApJ...916..103R

The effect of H₂ rovibrational excitation on the chemistry of protoplanetary disks is studied using a framework that solves for the disk physical and chemical structure and includes a detailed calculation of H₂ level populations. Chemistry with rovibrationally excited H₂ is found to be important for the formation of several commonly observed species in disks and this work demonstrates the need to accurately treat photon-dominated-region chemistry in disks if we are to make inferences on the chemical state of the disk during planet formation epochs. This is found to be even more critical for molecules like C₂H, CN, or HCN that are commonly used to infer changes in the elemental disk C/O and N/O ratios, with implications for planetesimal formation and the composition of exoplanet atmospheres. Computed vertical column densities with the full H₂ population calculation are increased by ∼1-2 orders of magnitude for molecules such as CN and HCN/HNC compared to calculations with no treatment of excited H₂. For the commonly used pseudo-level approximation, the computed columns of these molecules are overestimated by a factor of ∼3-5 when compared to the full model. We further note that the computed abundance for these molecules strongly depends on the strength of the FUV photons at energies that pump H₂ (i.e., 11-13.6 eV), which is not well constrained in disks, and that rate constants as a function of H₂ rovibrational levels for the key reaction N + H₂ - NH are needed for a more accurate assessment of CN/HCN chemistry but are currently unavailable.