Density Functional Theory for Transition Metals and Transition Metal Chemistry
REVIEW ARTICLE www.rsc.org/pccp | Physical Chemistry Chemical Physics Density functional theory for transition metals and transition metal chemistry Christopher J. Cramer* and Donald G. Truhlar* Received 8th April 2009, Accepted 20th August 2009 First published as an Advance Article on the web 21st October 2009 DOI: 10.1039/b907148b We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids. 1. Introduction chemical systems, in part because its cost scales more favorably with system size than does the cost of correlated WFT, and yet Density functional theory (DFT) describes the electronic states it competes well in accuracy except for very small systems. This of atoms, molecules, and materials in terms of the three- is true even in organic chemistry, but the advantages of DFT dimensional electronic density of the system, which is a great are still greater for metals, especially transition metals. The simplification over wave function theory (WFT), which involves reason for this added advantage is static electron correlation. a3N-dimensional antisymmetric wave function for a system It is now well appreciated that quantitatively accurate 1 with N electrons. Although DFT is sometimes considered the electronic structure calculations must include electron correlation. B ‘‘new kid on the block’’, it is now 45 years old in its modern It is convenient to recognize two types of electron correlation, 2 formulation (more than half as old as quantum mechanics the first called dynamical electron correlation and the second 3,4 itself), and it has roots that are almost as ancient as the called static correlation, near-degeneracy correlation, or non- Schro¨ dinger equation.
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