A quantum dynamical study of the rotation of the dihydrogen ligand in the Fe(H)₂(H₂)(PEtPh₂)₃ coordination complex

Progress in the hydrogen fuel field requires a clear understanding and characterization of how materials of interest interact with hydrogen. Due to the inherently quantum mechanical nature of hydrogen nuclei, any theoretical studies of these systems must be treated quantum dynamically. One class of material that has been examined in this context are dihydrogen complexes. Since their discovery by Kubas in 1984, many such complexes have been studied both experimentally and theoretically. This particular study examines the rotational dynamics of the dihydrogen ligand in the Fe(H)₂(H₂)(PEtPh₂)₃ complex, allowing for full motion in both the rotational degrees of freedom and treating the quantum dynamics (QD) explicitly. A "gas-phase" global potential energy surface is first constructed using density functional theory with the Becke, 3-parameter, Lee-Yang-Parr functional; this is followed by an exact QD calculation of the corresponding rotation/libration states. The results provide insight into the dynamical correlation of the two rotation angles as well as a comprehensive analysis of both ground- and excited-state librational tunneling splittings. The latter was computed to be 6.914 cm^-1-in excellent agreement with the experimental value of 6.4 cm^-1. This work represents the first full-dimensional ab initio exact QD calculation ever performed for dihydrogen ligand rotation in a coordination complex.