Protonated phosphorus mononitride: Spectroscopic parameters and formation routes relevant for astrochemistry

Abstract

Phosphorus-bearing molecules are of growing interest in astrochemistry because of the essential role of phosphorus in biochemistry. Understanding their interstellar chemistry requires both accurate spectroscopic data and insights into their formation mechanisms. In this work, for a new possible phosphorus-bearing species, protonated phosphorus mononitride, PNH+, we present a high-level theoretical study, which combines an accurate spectroscopic characterization with a thermochemical and kinetic investigation of its formation pathways. The key spectroscopic parameters, computed by exploiting composite schemes rooted in coupled-cluster theory, refer to both rotational and vibrational spectroscopy, thus including rotational and centrifugal distortion constants, hyperfine parameters, as well as vibrational frequencies and infrared intensities. To assess their accuracy for PNH+, a comparison with those of the isovalent N2H+, HCO+, and HCS+ ions, whose experimental characterization is available, has been made. In parallel, we investigated three gas-phase formation reactions relevant to interstellar conditions: the protonation of PN by H3+ and the ion–neutral PH + NH+ and PH+ + NH reactions. For each process, the reactive potential energy surface is sampled using density functional theory, and reaction rate coefficients are derived from long-range capture theory and master equation analysis. These rates were then incorporated into a dedicated astrochemical model to discuss the expected abundance of PNH+ in the interstellar medium. The results show that, under interstellar conditions, multiple exothermic pathways can lead to PNH+, thus reinforcing its potential role in interstellar phosphorus chemistry.