Toward accurate theoretical thermochemistry of first row transition metal complexes.

Abstract

The recently developed correlation consistent Composite Approach for transition metals (ccCA-TM) was utilized to compute the thermochemical properties for a collection of 225 inorganic molecules containing first row (3d) transition metals, ranging from the monohydrides to larger organometallics such as Sc(C(5)H(5))(3) and clusters such as (CrO(3))(3). Ostentatiously large deviations of ccCA-TM predictions stem mainly from aging and unreliable experimental data. For a subset of 70 molecules with reported experimental uncertainties less than or equal to 2.0 kcal mol(-1), regardless of the presence of moderate multireference character in some molecules, ccCA-TM achieves transition metal chemical accuracy of ±3.0 kcal mol(-1) as defined in our earlier work [J. Phys. Chem. A2007, 111, 11269-11277] by giving a mean absolute deviation of 2.90 kcal mol(-1) and a root-mean-square deviation of 3.91 kcal mol(-1). As subsets are constructed with decreasing upper limits of reported experimental uncertainties (5.0, 4.0, 3.0, 2.0, and 1.0 kcal mol(-1)), the ccCA-TM mean absolute deviations were observed to monotonically drop off from 4.35 to 2.37 kcal mol(-1). In contrast, such a trend is missing for DFT methods as exemplified by B3LYP and M06 with mean absolute deviations in the range 12.9-14.1 and 10.5-11.0 kcal mol(-1), respectively. Salient multireference character, as demonstrated by the T(1)/D(1) diagnostics and the weights (C(0)(2)) of leading electron configuration in the complete active self-consistent field wave function, was found in a significant amount of molecules, which can still be accurately described by the single reference ccCA-TM. The ccCA-TM algorithm has been demonstrated as an accurate, robust, and widely applicable model chemistry for 3d transition metal-containing species with versatile bonding features.