Accurate thermochemistry for transition metal complexes from first-principles calculations

摘要

The "correlation consistent Composite Approach" or ccCA is an ab initio model chemistry based on the single reference MP2 level of theory. By adjusting the basis set and level of theory of the core valence additive correction, ccCA is capable of reliable thermochemical predictions of inorganic and organometallic transition metal-containing molecules, as well as achieving chemical accuracy on main group species, with a mean absolute deviation of 0.89 kcal mol-1 against the 147 enthalpies of formation in the G2/97 test set. For a set of 52 complexes containing elements Sc-Zn, ranging in size from diatomics to Ni (PF_3) _4 and Fe (C_5 H_2) _2, ccCA on average predicts enthalpies of formation to within ±3 kcal mol-1 of the experimental result with a mean absolute deviation of 2.85 kcal mol-1 and a root mean square deviation of 3.77 kcal mol-1. The ccCA methodology is a significant step toward quantitative theoretical modeling of transition metal thermodynamics.