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.
The utility of several nonhybrid density functional approximations (DFAs) is considered for the prediction of gas phase enthalpies of formation for a large set of 3d transition metal-containing molecules. Nonhybrid DFAs can model thermochemical values for 3d transition metal-containing molecules with accuracy comparable to that of hybrid functionals. The GAM-generalized gradient approximation (GGA); the TPSS, M06-L, and MN15-L meta-GGAs; and the Rung 3.5 PBE+ΠLDA(s) DFAs all give root-mean-square deviations below that of the widely used B3LYP hybrid. Modern nonhybrid DFAs continue to show utility for transition metal thermochemistry.
Gold's structure-dependent catalytic activity motivates the study of reactions on a range of gold nanostructures. Electronic structure methods used to model gold catalysis should be capable of treating atoms, clusters, nanostructures, and surfaces on an equal theoretical footing. We extend our previous density functional theory (DFT) studies of a model reaction, H 2 adsorption and dissociation on unsupported Au 3 clusters [J. Phys. Chem. C 2013, 117, 7487], to larger clusters, quasi-one-dimensional nanowires and nanoribbons, and surfaces. We focus on trends in DFT predictions made using various approximate exchange-correlation functionals. Most functionals predict qualitatively reasonable trends, i.e., decreasing adsorption energies and increasing dissociation barriers with increasing Au coordination number. However, significant quantitative differences motivate continued exploration of methods beyond the generalized gradient approximation.
Substituent effects on the π-π interactions of aromatic rings are a topic of much recent debate. Real substituents give a complicated combination of inductive, resonant, dispersion, and other effects. To help partition these effects, we present calculations on fictitious "pure" σ donor/acceptor substituents, hydrogen atoms with nuclear charges other than 1. "Pure" σ donors with nuclear charge <1 weaken π-π stacking in the sandwich benzene dimer. This result is consistent with the electrostatic model of Hunter and Sanders, and different from real substituents. Calculated inductive effects are largely additive and transferable, consistent with a local direct interaction model. A second series of fictitious substituents, neutral hydrogen atoms with an artificially broadened nuclear charge distribution, give similar trends though with reduced additivity. These results provide an alternative perspective on substituent effects in noncovalent interactions.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.