Molybdenum-Sulfur Bond: Electronic Structure of Low-Lying States of MoS.

Abstract

The molybdenum-sulfur bond plays an important role in many processes such as nitrogen-fixation, and it is found as a building block in layered materials such as MoS2, known for its various shapes and morphologies. Here, we present an accurate theoretical and experimental investigation of the chemical bonding and the electronic structure of 20 low-lying states of the MoS molecule. Multireference and coupled cluster methodologies, namely, MRCISD, MRCISD + Q, RCCSD(T), and RCCSD[T], were employed in conjunction with basis sets up to aug-cc-pwCV5Z-PP/aug-cc-pwCV5Z for the study of these states. We note the significance of including the inner 4s24p6 electrons of Mo and 2s22p6 of S in the correlated space to obtain accurate results. Experimentally, the predissociation threshold of MoS was measured using resonant two-photon ionization spectroscopy, allowing for a precise measurement of the bond dissociation energy. Our extrapolated computational D0 value for the ground state is 3.936 eV, in excellent agreement with our experimental measurement of 3.932 ± 0.004 eV. The largest calculated adiabatic D0 (5.74 eV) and the largest dipole moment (6.50 D) were found for the 5Σ+ state, where a triple bond is formed. Finally, the connection of the chemical bonding of the isolated MoS species to the relevant solid, MoS2, is emphasized. The low-lying septet states of the diatomic molecule are involved in the material as a building block, explaining the stability and the variety of the shapes and morphologies of the material.