Electronic Structure of the Ground and Low-Lying States of MoLi

Molybdenum lithium compounds and materials are being researched and applied in cutting-edge industries; however, their bonding has not been explored in a systematic way. The present study investigates the MoLi molecule, to shed light on its bonding. Specifically, the electronic structure and bonding of the ground and 40 low-lying states of the MoLi molecule are explored, employing multireference methodologies, i.e., CASSCF and MRCISD(+Q) in conjunction with the aug-cc-pV5z(-PP) basis set. Bond distances, dissociation energies, dipole moments as well as common spectroscopic constants are given, while the potential energy curves are plotted. For the ground state, X${}_6{}^{}{\mathsf{\Sigma }}^{+}$, it is found that ${\mathrm{R}}_{\mathrm{e}}$ = 2.708 Å, ${\mathrm{D}}_{\mathrm{e}}$ = 24.1 kcal/mol, ${\mathsf{\omega }}_{\mathrm{e}}$ = 316.8 ${\mathrm{cm}}^{-1}$, ${\mathsf{\omega }}_{\mathrm{e}}{\mathrm{x}}_{\mathrm{e}}$ = 2.11 ${\mathrm{cm}}^{-1}$, and μ = 3.63 D. Overall, the calculated states present a variety of bonds, from weak van der Waals up to the formation of 2.5 bonds. The dissociation energies of the calculated states range from 2.3 kcal/mol ($\mathrm{a}{}^8\mathsf{\Sigma }^{+}$) to 34.7 ($\mathrm{c}{}^4\mathsf{\Pi }$), while the bond distances range from 2.513 Å to 3.354 Å. Finally, dipole moment values up to 3.72 D are calculated. In most states, a 2s${2\mathrm{p}}_{\mathrm{z}}$ hybridization on Li and a ${4\mathrm{d}}_{{\mathrm{z}}^2}$5s${5\mathrm{p}}_{\mathrm{z}}$ or 5s${5\mathrm{p}}_{\mathrm{z}}$ hybridization on Mo are found. Moreover, it is observed that the excited Li(${}^2\mathrm{P}$) atom forms the shortest bonds because its empty ${2\mathrm{s}}^0$ orbital can easily accept electrons, resulting in a strong σ dative bond. Finally, the present work highlights the exceptional ability of lithium atoms to participate in a variety of bonding schemes, and it could provide the opening gate for further investigation of this species or associated material and complexes.