Insights into the Molecular Structure and Spectroscopic Properties of HONCO: An Accurate Ab Initio Study

[Image: see text] In an effort to provide the first accurate structural and spectroscopic characterization of the quasi-linear chain HONCO in its electronic ground state, state-of-the-art computational approaches mainly based on coupled-cluster (CC) theory have been employed. Equilibrium geometries have been calculated by means of a composite scheme based on CC calculations that incorporates up to the quadruple excitations and accounts for the extrapolation to the complete basis set limit and core correlation effects. This approach is proven to provide molecular structures with an accuracy better than 0.001 Å and 0.05° for bond lengths and angles, respectively. Incorporation of vibrational effects permits this level of theory to predict rotational constants with an estimated accuracy of 0.1% or better. Vibrational fundamental bands have been evaluated by means of a hybrid scheme based on harmonic frequencies computed using the CC singles, doubles, and a perturbative treatment of the triples method (CCSD(T)) in conjunction with a quadruple-ζ basis set, with all electrons being correlated, and anharmonic corrections from CCSD(T) calculations using a triple-ζ basis set, within the frozen-core approximation. Such a hybrid approach allowed us to obtain fundamental frequencies with a mean absolute error of about 1%. To complete the spectroscopic characterization, vertical electronic excitation energies have been calculated for the lowest singlet and triplet states using the internally contracted multireference configuration interaction (MRCI) method. Computations show that HONCO dissociates into OH + NCO upon the absorption of UV–vis light. In conclusion, we are confident that the highly accurate spectroscopic data provided herein can be useful for guiding future experimental investigations and supporting the characterization of this molecule in atmospheric and astrophysical media, as well as in combustion.