Analysis of chemical bonding of the ground and low-lying states of Mo2 and of Mo2Clx complexes, x = 2–10

Abstract

In this study, we perform accurate calculations via multireference configuration interaction and coupled cluster methodologies on the dimolybdenum molecule in conjunction with complete series of correlation and weighted core correlation consistent basis sets up to quintuple size. The bonding, the dissociation energies, and the spectroscopic parameters of the seven states that correlate with the ground state products are calculated. The ground state has a sextuple chemical bond, and each of the calculated excited states has one less bond than the previous state. The calculated values for the ground [Formula: see text] state of Mo2 have been extrapolated to the complete basis set limits. Our final values, re = 1.9324 Å and De (D0) = 4.502 ± 0.007(4.471 ± 0.009) eV, are in excellent agreement with the experimental values of re = 1.929, 1.938(9) Å and D0 = 4.476(10) eV. Mo2 in the [Formula: see text] state is a weakly bound dimer, forming 5s⋯5pz bonds, with De = 0.120 eV at re = 3.53 Å. All calculated excited states (except [Formula: see text]) have a highly multireference character (C0 = 0.25–0.55). The ordering of the molecular bonding orbitals changes as the spin is increased from quintet to septet state resulting in a change in energy separation [Formula: see text]S,S−1 of the calculated states. The quite low bond dissociation energy of the ground state is due to the splitting of the molecular bonding orbitals in two groups differing in energy by ∼3 eV. Finally, the bond breaking of Mo2, as the multiplicity of spin is increased, is analyzed in parallel with the Mo–Mo bond breaking in a series of Mo2Clx complexes when x is increased. Physical insight into the nature of the sextuple bond and its low dissociation energy is provided.