Interaction averaged electrostatic

The most elementary mean-field models of electronic structure introduce a potential that an electron at r would experience if it were interacting with a spatially averaged electrostatic charge density arising from the N- 1 remaining electrons ... 

Table 1. Average ligand-surrounding interaction energies, electrostatic corrections and observed binding free energies (kcal/mol) for the eight thrombin inhibitors (from Ref. 46). b...

The polarity of a solid surface can be regarded as the strength of its average electrostatic field F. This field interacts with permanent or induced dipoles of adsorbed molecules, whereas its gradient interacts with permanent or induced quadrupoles. These interactions give rise to components of the adsorption energy such as EFfl (with permanent dipoles), Ef (polarization contribution) or PQ (with permanent quadrupoles). Therefore, the selection of the appropriate immersion systems, differing mainly in the molecular dipole moment n of the immersion liquid, can be expected to provide information on the value of EPfl since ... 

The terms included in equation 2, are respectively the kinetic operator, the attraction of a single electron with all nuclei centered in all cells, the averaged electrostatic potential of all electrons and the averaged exchange interaction. 

In sec. 1.4.3c we have already introduced the mean (average) electrostatic potential. The mean electrostatic potential yr x ) is related to the work necessary to bring an Infinitely small probe charge from Infinity to Xj without disturbing the environment. This potential can be defined In terms of the one- and two-body interactions, mentioned above, according to... 

Equation (a), with set equal to ( >, is surprisingly successful in describing the effect of varying the double-layer structure upon the kinetics of electrochemical reactions at Hg electrodes, at least in the absence of specific adsorption of the supporting electrolyte (i.e., when the inner-layer region adjacent to the electrode contains only solvent molecules). However, this does not necessarily imply that average electrostatic interactions provide the sole contribution to the work terms, because contributions may arise from other sources that remain constant under these conditions. In particular, inner-sphere pathways commonly involve reaction sites within the outer Helmholtz plane. Consequently, the overall work terms consist of separate contributions from transporting the reactant from the bulk solution to this outer plane and from this plane to the reaction site within the inner layer. The latter will then be independent of and, therefore, influence only k j.. in Eq. (a). 

If the work terms can be described by average electrostatic interactions, then, Wp = Because for a one-electron reduction the product charge number is... 

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