Numerical basis functions anion

In order to estimate the reliability of the pseudopotential variant of our DVM package [40], [54], [55], the molecules O2, O3, CI2 as well as the complex anions PdCl and PdCl are considered. The following valence configurations of the neutral atoms were assumed O (2s 2p ), Cl (3s 3p ), and Pd (4p 4d 5s ) when constructing the pseudopotentials, and the a parameters are the Schwartz s [56] ones. We made use of the numerical pseudoorbitals as the basis functions. Several calculations were performed with adding some diffuse STOs from Roetti-Clementi s double- basis [57] to our numerical bases. 

In light of previous discussion, positive HOMO eigenvalues do not appear to be fatal for DFT anion calculations, and thus another approach is simply to charge ahead but benchmark thoroughly. To this end, Schaefer and coworkers have benchmarked the performance of numerous density-functionals and basis sets against a data set consisting of 91 AEAs that have been determined, using photoelectron spectroscopy, to an accuracy of better than 0.09 eV. (On the... 

Figure 12. Relative energies (kcal/mol) of the Fj anion, as functions of the F-F distance. All calculations are performed at the PP level, using the (5,2 5,2) and IGLO-III basis sets. The three curves included are obtained using slightly different procedures for the fitting of Yxc 32 radial shells (solid line), 64 radial shells (dashed line), and 32 radial shells + extra numerical iteration after the SCF step (semi-dashed line).

In what follows, we propose a phenomenological model of the chemisorbed radical-anion standing in the electrochemical double-layer. We shall hence detail the reasons why this chemisorbed radical anion is intrinsically unstable but most probably has a finite lifetime on the polarized metallic surface. We outline the procedure through which we expect that an order of magnitude of the lifetime of the chemisorbed radical-anion may be evaluated numerically via this model. The model potential felt by the radical-anion as it is formed on the polarized electrode is described as the sum of three terms, for which a parametrisation is proposed. One of these terms is meant to include both the surrounding solvent and the repulsion by the polarized electrode, thanks to a mean, locally uniform, electric field. In the present paper, the intensity of this uniform electric field is calibrated on the basis of a conparison between experimental Stark-Tuning shifts for CO chemisorbed on palladium surfaces in solution and Density Functional Theory calculations of field-induced vibrational shifts for CO chemisorbed on palladium clusters. The shape of the resulting model potential is then discussed. 

The latex particles further allow us to examine directly the Smoluchowski equation on binary collision, which is a basis of chemical kinetics (10). By counting the number of dimeric pairs of two different kinds of latices under the microscope as a function of time, the rate constant of the collision was estimated. Table 1 shows the numerical data for a set of cationic and anionic latices. The experimental value for the forward rate constant (kj.) was of the same order of magnitude as the theoretical value shown in brackets, but always smaller than the latter, though the latices were oppositely charged. The reason for this difference is being cons i dered. 

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