Johnson E.R.(Ed.). Density Functionals. Thermochemistry

Springer – Cham, Heidelberg, New York, Dordrecht, London. 2015. — 189 p. (Topics in Current Chemistry 365) ISBN: 978-3-319-19691-6, doi: 10.1007/978-3-319-19692-3.Density-functional theory (DFT) has its roots in the works of Hohenberg and Kohn, Kohn and Sham, and Slater. Despite rumors of its untimely demise, DFT is presently enjoying ever greater application across a wide range of scientific disciplines, including chemistry, physics, biochemistry, and engineering. While density-functional approximations can be used for calculation of accurate structural and spectroscopic properties, they are most widely used for thermochemical predictions, such as heats of reaction, which are the subject of the present volume. Becke’s article applying gradient-corrected functionals to the “G1” set of atomization energies was the key study which first attracted the interest of the computational-chemistry community to density-functional theory. The subsequent implementation and testing in the Gaussian-92/DFT electronic-structure program marked the point where density functionals became a practical and attractive alternative to correlated-wavefunction theory for reaction thermochemistry.
Because of their high accuracy and computational efficiency, DFT methods have become the standard approach for thermochemical predictions. Generalized gradient approximations (GGAs) and hybrid functionals are now implemented in a variety of commercial and open-source electronic-structure programs which can be readily used by chemical researchers. In recent years, several other classes of functionals have been proposed.
The first few chapters give overviews of density-functional approximations as they currently stand and push the boundaries of their applicability to increasingly complex systems, consisting of very large molecules (Chap. 1), surface chemistry (Chap. 2), and van der Waals dimers (Chap. 3). Next, we address the problems associated with judging the relative quality of functionals (Chap. 4). Finally, we consider research on non-conventional functionals, including recent successes of random-phase approximations for thermochemistry (Chap. 5), spin-density functionals and issues with derivative discontinuities (Chap. 6), and real-space strongcorrelation models for exact-exchange-based DFT (Chap. 7), which may represent the future of the field.o Accurate Thermochemistry for Large Molecules with Modern Density Functionals. Marc Steinmetz, Andreas Hansen, Stephan Ehrlich, Tobias Risthaus, and Stefan Grimme.
o Density Functional Theory Beyond the Generalized Gradient Approximation for Surface Chemistry. Benjamin G. Janesko
o Short-Range Cut-Off of the Summed-Up van der Waals Series: Rare-Gas Dimers. Abhirup Patra, Bing Xiao, and John P. Perdew.
o Judging Density-Functional Approximations: Some Pitfalls of Statistics. Andreas Savin and Erin R. Johnson.
o The Ring and Exchange-Ring Approximations Based on Kohn–Sham Reference States. Andreas Heßelmann.
o Non-analytic Spin-Density Functionals. Martın A. Mosquera and Adam Wasserman.
o Fractional Kohn–Sham Occupancies from a Strong-Correlation. Density Functional. Axel D. Becke.