We present a systematic density functional investigation on the prediction of the 13C, 15N, 17O, and 19F NMR properties of 23 molecules with 21 density functionals. Extensive comparisons are made for both 13C magnetic shieldings and chemical shifts with respect to the gas phase experimental data and the best CCSD(T) results. We find that the OPBE and OPW91 exchange-correlation functionals perfo...

Meta-generalized gradient approximation (meta-GGA) exchange-correlation density functionals depend on the Kohn-Sham (KS) orbitals through the kinetic energy density. The KS orbitals in turn depend functionally on the electron density. However, the functional dependence of the KS orbitals is indirect, i.e., not given by an explicit expression, and the computation of analytic functional derivativ...

Due to the severe self-interaction errors associated with some density functional approximations, conventional density functionals often fail to dissociate the hemibonded structure of the water dimer radical cation (H(2)O)(2)(+) into the correct fragments: H(2)O and H(2)O(+). Consequently, the binding energy of the hemibonded structure (H(2)O)(2)(+) is not well-defined. For a comprehensive comp...

In existing game models, total functionals have no simple characterization neither in term of game strategies, nor in term of the total set-theoretical functionals they de ne. We show that the situation changes if we extend the usual notion of game by allowing in nite plays. Total functionals are, now, exactly those having a tree-strategy in which all branches end in a last move, winning for th...

Consequences of anisotropy (variation of orbital occupation) and magnetism, and their coupling, are analyzed for LSDA+U functionals, both the commonly used ones as well as less commonly applied functionals. After reviewing and extending some earlier observations for an isotropic interaction, the anisotropies are examined more fully and related to use with the local density (LDA) or local spin d...

We present the WCCR10 data set of 10 ligand dissociation energies of large cationic transition metal complexes for the assessment of approximate exchange-correlation functionals. We analyze nine popular functionals, namely BP86, BP86-D3, B3LYP, B3LYP-D3, B97-D-D2, PBE, TPSS, PBE0, and TPSSh by mutual comparison and by comparison to experimental gas-phase data measured with well-known precision....

The influence of the choice of the exchange-correlation functional (semilocal gradient corrected or hybrid functionals) on the electronic properties of metal-exchanged zeolites has been investigated for Cu- and Co-exchanged chabazite. The admixture of exact exchange in hybrid functionals increases the fundamental gap of purely siliceous chabazite, leading to better agreement with experiment and...

The Heyd-Scuseria-Ernzerhof (HSE) density functionals are popular for their ability to improve upon the accuracy of standard semilocal functionals such as Perdew-Burke-Ernzerhof (PBE), particularly for semiconductor band gaps. They also have a reduced computational cost compared to hybrid functionals, which results from the restriction of Fock exchange calculations to small inter-electron separ...

Different extentons of an isomorphism theorem of Dynkin are developed and are used to study two distinct but related families of functionals of Lévy processes; n-fold “near-intersections” of a single Lévy process, which is also referred to as a self-intersection local time, and continuous additive functionals of several independent Lévy processes. Intersection local times for n independent Lévy...

The theory of self-scaled conic programming provides a uniied framework for the theories of linear programming, semideenite programming and convex quadratic programming with convex quadratic constraints. Nesterov and Todd's concept of self-scaled barrier functionals allows the exploitation of algebraic and geometric properties of symmetric cones in certain variants of the barrier method applied...