Synthesis of organo-phosphorous species in space: the reaction of P$^+$ with C$_2$H$_2$

Abstract

Despite its low cosmic abundance, phosphorus is a bioessential element whose prebiotic availability and incorporation into biomolecules remain open questions. Only a few phosphorous containing molecules with P to C bonds have been detected in astronomical environments (CP, CCP, HCP). More complex species have been proposed, but their formation and destruction pathways remain poorly constrained. Gas-phase ion molecule chemistry involving P cations may contribute to organophosphorus formation, particularly in protostellar shocks and outflows, while reactions of ground state P cations with closed-shell neutrals provide benchmarks for spin-forbidden mechanisms. We investigate the reaction of P+ with C$_2$H$_2$ through a joint experimental and theoretical study aimed at revising astrochemical database rate coefficients. Absolute cross sections and branching ratios were measured as a function of collision energy and complemented by high-level electronic structure calculations and a refined capture model accounting for higher-order long-range interactions and intermediate complex formation. Channel-specific rate coefficients were derived in the range from 10 to 5000 K. The reaction produces predominantly HCCP$^+$ + H (branching ratio 99%), while CCP$^+$ + H$_2$ is a minor channel (branching ratio 1%) arising from intersystem crossing from the triplet to the singlet potential energy surfaces. The total rate coefficient at 300 K agrees well with the SIFT value, but it increases with decreasing temperature, deviating from a pure Langevin trend. The reaction should be included in astrochemical models where phosphorus is released as P+, such as during energetic processing of icy grains in shocks. It provides a pathway to linear HCCP$^+$, a potentially relevant precursor to the observed CP and CCP species through dissociative recombination