In a previous contribution (Mol. Phys. 103, xxxx, 2005), we established the suitability of density functional theory (DFT) for the calculation of molecular anharmonic force fields. In the present work, we have assessed a wide variety of basis sets and exchange-correlation functionals for harmonic and fundamental frequencies, equilibrium and ground-state rotational constants, and thermodynamic f...

Accurate description of hydrogen-bonding energies between water molecules and van der Waals interactions between guest molecules and host water cages is crucial for study of methane hydrates (MHs). Using high-level ab initio MP2 and CCSD(T) results as the reference, we carefully assessed the performance of a variety of exchange-correlation functionals and various basis sets in describing the no...

Molecular chemisorption at a metal surface is a key step for many processes, such as catalysis, electrochemistry, surface treatment, tribology and friction. Modeling with density functional theory is largely used on these systems. From a detailed comparison with accurate micro-calorimetric data on ten systems (involving ethylene, cyclohexene, benzene, naphthalene, CO, O2, H2, methane, ethane), ...

This paper generalizes Lyaponov functionals to the local setting, and it is shown that they may serve as a connection between Florack's et al. pseudo-linear scale-spaces and Koenderink's et al. local soft histograms. A generalized scale-selection method is proposed based on local Lyaponov functionals and local soft histograms, and it is shown that the method includes Lindebergs's Blob-detector ...

This paper investigates analogs of the Kreisel-Lacombe-Shoenfield Theorem in the context of the type-2 basic feasible functionals. We develop a direct, polynomial-time analog of effective operation in which the time boundingon computations is modeled after Kapron and Cook’s scheme for their basic polynomial-time functionals. We show that if P = NP, these polynomial-time effective operations are...

This paper deals with the quantitative normal approximation of non-linear functionals of Poisson random measures, where the quality is measured by the Kolmogorov distance. Combining Stein’s method with the Malliavin calculus of variations on the Poisson space, we derive a bound, which is strictly smaller than what is available in the literature. This is applied to sequences of multiple integral...

We propose a new simple scheme for self-interaction correction (SIC) of exchange functionals in the density functional theory. In the new scheme, exchange energies are corrected by substituting exchange self-interactions for exchange functionals in regions of self-interaction. To classify the regions of self-interaction, we take advantage of the property of the total kinetic energy density appr...

In this paper we develop an approach to the notion of computable functionals in a very abstract setting not restricted to Turing or, say, polynomial computability. We assume to start from some basic class of domains and a basic class of functions deened on these domains. (An example may be natural numbers with polytime computable functions). Then we deene what are \all" corresponding functional...

We introduce two new functionals, the constrained covariance and the kernel mutual information, to measure the degree of independence of random variables. These quantities are both based on the covariance between functions of the random variables in reproducing kernel Hilbert spaces (RKHSs). We prove that when the RKHSs are universal, both functionals are zero if and only if the random variable...

The main goal of this article is to introduce a new notion of qualitative robustness that applies also to tail-dependent statistical functionals and that allows us to compare statistical functionals in regards to their degree of robustness. By means of new versions of the celebrated Hampel theorem, we show that this degree of robustness can be characterized in terms of certain continuity proper...