General Performance of Density Functionals

Abstract

The density functional theory (DFT) foundations date from the 1920s with the work of Thomas and Fermi, but it was after the work of Hohenberg, Kohn, and Sham in the 1960s, and particularly with the appearance of the B3LYP functional in the early 1990s, that the widespread application of DFT has become a reality. DFT is less computationally demanding than other computational methods with a similar accuracy, being able to include electron correlation in the calculations at a fraction of time of post-Hartree-Fock methodologies. In this review we provide a brief outline of the density functional theory and of the historic development of the field, focusing later on the several types of density functionals currently available, and finishing with a detailed analysis of the performance of DFT across a wide range of chemical properties and system types, reviewed from the most recent benchmarking studies, which encompass several well-established density functionals together with the most recent efforts in the field. Globally, an overall picture of the level of performance of the plethora of currently available density functionals for each chemical property is drawn, with particular attention being dedicated to the relative performance of the popular B3LYP density functional.

Silica Surface Features and Their Role in the Adsorption of Biomolecules: Computational Modeling and Experiments

“…385 At variance with the GGA case, the implementation of hybrid functionals is easier using localized basis functions (Gaussian type orbitals, vide infra). To show an example of the DFT performance with respect to the present topic, the structural data and relative stabilities of -quartz, -cristobalite and -tridymite 386,306 are very well reproduced with B3LYP with a 6-31G(d) Guassian basis, as illustrated in Table 2.…”

Distributed Atomic Polarizabilities of Amino Acids and their Hydrogen-Bonded Aggregates

“…We have evaluated the performances of the most popular density functionals for the calculation of distributed polarizabilities. The main features of the DFT schemes under investigation are described in the Supporting Information, classified according to Sousa et al 54 As discussed in the previous section, MP2 is taken as benchmark. The comparisons refer to calculations performed using the d-aug-cc-pVTZ basis set, one of the most complete basis set applied in this study, certainly guaranteeing basis-set convergence as discussed in the previous section.…”

Recent Progresses in Understanding of Co-Based Fischer–Tropsch Catalysis by Means of Transient Kinetic Studies and Theoretical Analysis

“…2. With the advancement of sophisticated computational chemistry techniques, the intricate electronic-structure calculations based on density functional theory (DFT) have recently been widely used to provide fundamental data regarding the surface reaction, which can be a complement to the experimental analysis for understanding of reaction mechanisms [23][24][25][26]. More importantly, it can distinguish between those possibilities that were left open, such as various reaction pathways.…”

“…Since the mechanism of FTS is inconclusive and controversial, more and more DFT calculations have been devoted to tackle these issues [18,19], especially for the mechanism of CO activation [27][28][29][30][31], methane formation [32][33][34][35], and chain growth [36][37][38]. Despite the successful implementations of DFT in catalysis process, it still holds some drawbacks such as failure in the calculation of weak interactions (such as Van der Waals interaction) [25]. Fortunately, DFT calculations in combination with experimental work (such as spectroscopic methods and kinetic analysis), has proved to be a more powerful tool in modelling active sites and exploring the mechanism at a molecular level.…”