On the formation of 2- and 3-cyanofurans and their protonated forms in interstellar medium conditions: quantum chemical evidence

The literature is still poor in theoretical and experimental, including both spectroscopic and thermodynamic data for protonated furan and protonated 2-cyanofuran and 3-cyanofuran (FH(+), 2CFH(+) and 3CFH(+)). These data are, however, crucial for astrophysicists and astrochemists in the detection of new species in interstellar medium (ISM), the discovery of these molecular species being not yet reported. It is in this perspective that a computational study based on quantum chemistry on FH(+), 2CFH(+) and 3CFH(+) was undertaken. A series of properties including the proton affinity (PA) of furan and the two cyanofurans, the variations of enthalpy (Δ(r)H), entropy (Δ(r)S), and Gibbs free energy (Δ(r)G) for the reactions yielding cyanofurans (neutral and protonated forms), were studied at different temperatures (5 K, 10 K, 150 K and 298 K) and pressures (P = 1 atm and P = 10(−5) atm) based on modern computational models (G2MP2, G3, G4MP2 and G4). While confirming that the protonation favors the α-position for furan, the PA values show that the protonation favors the nitrogen atom in cases of 2CFH(+) and 3CFH(+). The Δ(r)H, Δ(r)S and Δ(r)G values revealed spontaneous reactions producing these species under ISM conditions of temperature and pressure. In addition quadrupole hyperfine structures and vibrational spectra which are essential tools for the characterization and the identification of interstellar molecular species are predicted, while the region where brightest lines fall for different temperatures is discussed. The results reported in this work are expected to assist astrophysicists and astrochemists, in the search for new chemical species in interstellar environments.