Theoretical Rovibrational Spectroscopy of Magnesium Tricarbide-Multireference Character Thwarts a Full Analysis of All Isomers.

Magnesium tricarbide isomers are studied herein with coupled cluster theory and multireference configuration interaction to support their possible detection in astrochemical environments such as the circumstellar envelope surrounding the star IRC +10216 or in terrestrial laboratories. Magnesium-bearing species may abound in the interstellar medium (ISM), but only eight (MgNC, MgCN, HMgNC, MgC 2 H, MgC 3 N, MgC 4 H, MgC 5 N, and MgC 6 H) have been directly identified thus far. Several possible isomers for the related MgC 3 system are explored in their singlet and triplet spin multiplicities. Overall, this work offers quantum chemical insight of rovibrational spectroscopic data for MgC 3 using quartic force fields (QFFs) based on the CCSD(T) and CCSD(T)-F12 levels of theory at the complete basis set (CBS) limit. Additional corrections with small basis set CCSDT(Q) and scalar relativistic effects are also included in the analysis. Salient multireference character is found in the singlet diamond electronic state, which makes a definitive assignment of the ground state challenging. Nevertheless, coupled cluster-based composite energies and multireference configuration interaction both predict that the 1 A 1 diamond isomer is 1.6-2.2 kcal mol -1 lower in energy than the 3 A 1 diamond isomer. Furthermore, highly accurate binding energies of various isomers MgC 3 are provided for comparison to photodetachment experiments. Dipole moments along with harmonic infrared intensities will guide efforts for astronomical and spectroscopic characterization.