Theoretical study of vibronic perturbations in magnesium carbide

<div><p>ABSTRACT</p><p>Understanding molecular systems with complex multi-configurational bonding has been of interest to both experimentalists and theoreticians for many years. High level dynamically weighted MRCI calculations were used to generate accurate potential energy curves for the triplet ground state <sup>3</sup>Σ<sup>−</sup>, and triplet excited states up to (4 <sup>3</sup>Σ<sup>−</sup>, 4 <sup>3</sup>Π and 1 <sup>3</sup>Δ) and quintet (1 <sup>5</sup>Σ<sup>−</sup> and 1 <sup>5</sup>Π) states up to 50,000 cm<sup>−1</sup> above the ground state minimum. The lowest four <sup>3</sup>Π states of magnesium mono-carbide (MgC) are strongly coupled leading to lifetimes that are shortened by pre-dissociation for most of the vibronic states. Non-adiabatic derivative couplings between the <sup>3</sup>Π states were used to determine diabatic potential energy curves. The state mixing role of spin–orbit coupling, which is much weaker than the non-adiabatic interactions, is discussed. A coupled vibronic Hamiltonian was solved to compute and assign strongly mixed vibronic states. The results are compared and contrasted with the valence iso-electronic beryllium carbide (BeC) system whose results were published earlier [B.J. Barker, I.O. Antonov, J.M. Merritt, V.E. Bondybey, M.C. Heaven, and R. Dawes, <i>J. Chem. Phys</i>. <b>137</b>, 214313 (2012)]. Transitions, spectroscopic constants and band origins are expected to aid experimental detection of MgC in the future.</p></div>