Formally, each orthogonalized-plane-wave basis function may be written as (1 - P), where ijjk is a plane wave and P is the projection operator such that Pif/k gives the core-state component of Il k [Pg.31]

Although the pseudopotential is, from its definition, a nonlocal operator, it is often represented approximately as a multiplicative potential. Parameters in some chosen functional form for this potential are chosen so that calculations of some physical properties, using this potential, give results agreeing with experiment. It is often the case that many properties can be calculated correctly with the same potential.43 One of the simplest forms for an atomic model effective potential is that of Ashcroft44 r l0(r — Rc), where the parameter is the core radius Rc and 6 is a step-function. [Pg.31]

One now has a picture of conduction electrons in the potential of the ions, which is really a collection of pseudopotentials. The energy of the electronic system obviously depends on the positions of the ions. From the electronic energy as a function of ionic positions, say Ue,(R), one could determine the equilibrium ionic configuration (interionic spacing in a crystal or ion density profile [Pg.31]

For simple monovalent metals, the pseudopotential interaction between ion cores and electrons is weak, leading to a uniform density for the conduction electrons in the interior, as would obtain if there were no point ions, but rather a uniform positive background. The arrangement of ions is determined by the ion-electron and interionic forces, but the former have no effect if the electrons are uniformly distributed. As the interionic forces are mainly coulombic, it is not surprising that the alkali metals crystallize in a body-centered cubic lattice, which is the lattice with the smallest Madelung energy for a given density.46 Diffraction measurements [Pg.32]

The linear dependence of C witii temperahire agrees well with experiment, but the pre-factor can differ by a factor of two or more from the free electron value. The origin of the difference is thought to arise from several factors the electrons are not tndy free, they interact with each other and with the crystal lattice, and the dynamical behaviour the electrons interacting witii the lattice results in an effective mass which differs from the free electron mass. For example, as the electron moves tlirough tiie lattice, the lattice can distort and exert a dragging force. [Pg.129]

Electrons interact with solid surfaces by elastic and inelastic scattering, and these interactions are employed in electron spectroscopy. For example, electrons that elastically scatter will diffract from a single-crystal lattice. The diffraction pattern can be used as a means of stnictural detenuination, as in FEED. Electrons scatter inelastically by inducing electronic and vibrational excitations in the surface region. These losses fonu the basis of electron energy loss spectroscopy (EELS). An incident electron can also knock out an iimer-shell, or core, electron from an atom in the solid that will, in turn, initiate an Auger process. Electrons can also be used to induce stimulated desorption, as described in section Al.7.5.6. [Pg.305]

This gives the total energy, which is also the kinetic energy in this case because the potential energy is zero within the box , m tenns of the electron density p x,y,z) = (NIL ). It therefore may be plausible to express kinetic energies in tenns of electron densities p(r), but it is by no means clear how to do so for real atoms and molecules with electron-nuclear and electron-electron interactions operative. [Pg.2181]

Baran P S, Monaco R R, Khan A U, Schuster D I and Wilson S R 1997 Synthesis and cation-mediated electronic interactions of two novel classes of porphyrin-fullerene hybrids J. Am. Chem. See. 119 8363-4... [Pg.2435]

Hamiltonians equivalent to (1) have been used by many authors for the consideration of a wide variety of problems which relate to the interaction of electrons or excitons with the locaJ environment in solids [22-25]. The model with a Hamiltonian containing the terms describing the interaction between excitons or electrons also allows for the use of NDCPA. For example, the Hamiltonian (1) in which the electron-electron interaction terms axe taken into account becomes equivalent to the Hamiltonians (for instance, of Holstein type) of some theories of superconductivity [26-28]. [Pg.445]

Above mathematics shows that the changes in the model Hamiltonian (1) that do not involve the exciton-phonon coupling terms, - for instance inclusion the exciton-exciton (electron-electron) interaction, lead only to the respective change of in Eqs.(16). [Pg.453]

In 1965, however, the computational resources needed for the full SCF approach were not yet available. Practical MO theories therefore still needed approximations. The main problem is the calculation and storage of the four-center integrals, denoted (fiv I Aa), needed to calculate the electron-electron interactions within the... [Pg.381]

Note This simple orbital interaction picture is nsefnl for interpreting results, bill neglects many aspects of a calcnlation, such as electron-electron interactions. These diagrams are closely related to the results from Extended Ilhckel calculations. [Pg.48]

Extended Hiickel is the simplest and fastest senii-empirical method included m IlyperC hem, but it isalso the least accurate. It Is particularly simple in its treatment of electron-electron interactions it has no explicit treatment of these interactions, although it may include some of their effects by parameteri/.aiioii. [Pg.125]

Tiere remain four integrals arising from electron-electron interactions. These are ... [Pg.64]

If vve now expand the expression for the energy as for the ground state, terms analogous to the electron-nucleus and electron-electron interactions can again be obtained. However, the cross-terms are no longer equal to zero as was the case for the ground state, because the... [Pg.65]

In the Hiickel or extended Hiiekel methods no explicit reference is made to electron-electron interactions although such contributions are absorbed into the V potential, and... [Pg.199]

C. Semi-Empirical Models that Treat Electron-Electron Interactions 1. The ZDO Approximation... [Pg.609]

Unlike the Hiickel and extended Hiickel methods, the semi-empirical approaches that explicitly treat electron-electron interactions give rise to Fock matrix element... [Pg.611]

One of the limitations of HF calculations is that they do not include electron correlation. This means that HF takes into account the average affect of electron repulsion, but not the explicit electron-electron interaction. Within HF theory the probability of finding an electron at some location around an atom is determined by the distance from the nucleus but not the distance to the other electrons as shown in Figure 3.1. This is not physically true, but it is the consequence of the central field approximation, which defines the HF method. [Pg.21]

Hartree-Fock (HF) an ah initio method based on averaged electron-electron interactions... [Pg.364]

This qualitative theory still provides the most widely used means for describing reactions in organic chemistry. Two principal modes of electronic interaction in organic molecules are recognised the inductive and mesomeric effects. [Pg.125]

S—Cg is perpendicular to the amide plane of the / -lactam and therefore weakened. The S—bond, on the other hand, is not affected by electronic interactions with the benzamide plane. It was now thought, that a bridging of the thiazolidine moiety would bring the —S bond into a more orthogonal position with respect to the amide plane of the new lactam and make this bond more fragile. The tricyclic thiazolidine was synthesized as described above and fulfilled the predictions (J.E. Baldwin, 1978). [Pg.315]

As a consequence of the rigid face-to-face orientation, there are strong electronic interactions between the benzene rings in the dibenzo-anellated isodrin derivative. Irradiation with 254-nm UV light gave rise to a 7 3 equilibrium mixture of the educt with the [6 -I- 6]cycloaddition isomer. At an irradiation wavelength of 300 nm the cycloaddition wa completely reversed. [Pg.336]

As shown m Figure 4 11 the crucial electronic interaction is between an unshared elec tron pair of Cl and the vacant 2p orbital of the positively charged carbon of (CH3)3C ... [Pg.158]

It IS not possible to tell by inspection whether the a or p pyranose form of a par ticular carbohydrate predominates at equilibrium As just described the p pyranose form IS the major species present m an aqueous solution of d glucose whereas the a pyranose form predominates m a solution of d mannose (Problem 25 8) The relative abundance of a and p pyranose forms m solution depends on two factors The first is solvation of the anomeric hydroxyl group An equatorial OH is less crowded and better solvated by water than an axial one This effect stabilizes the p pyranose form m aqueous solution The other factor called the anomeric effect, involves an electronic interaction between the nng oxygen and the anomeric substituent and preferentially stabilizes the axial OH of the a pyranose form Because the two effects operate m different directions but are com parable m magnitude m aqueous solution the a pyranose form is more abundant for some carbohydrates and the p pyranose form for others... [Pg.1040]

Cl calculations can be used to improve the quality of the wave-function and state energies. Self-consistent field (SCF) level calculations are based on the one-electron model, wherein each electron moves in the average field created by the other n-1 electrons in the molecule. Actually, electrons interact instantaneously and therefore have a natural tendency to avoid each other beyond the requirements of the Exclusion Principle. This correlation results in a lower average interelectronic repulsion and thus a lower state energy. The difference between electronic energies calculated at the SCF level versus the exact nonrelativistic energies is the correlation energy. [Pg.38]

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