Taking into account that it is necessary to make vary the flaw detector settings during the main part of the verifications, the total number of verifications is rather important. So, Technical Center for Mechanical Industries (CETIM) began the development of an electronic system enabling to benefit of the current possibilities of generation of synthesised radio frequency signals and help of personal computer for operator assistance and calculation. [Pg.703]

For many-electron systems such as atoms and molecules, it is obviously important that approximate wavefiinctions obey the same boundary conditions and symmetry properties as the exact solutions. Therefore, they should be antisynnnetric with respect to interchange of each pair of electrons. Such states can always be constmcted as linear combinations of products such as... [Pg.31]

Regardless of how many single-particle wavefiinctions i are available, this number is overwhelmed by the number of n-particle wavefiinctions ( ) (Slater detenninants) that can be constructed from them. For example, if a two-electron system is treated within the Flartree-Fock approximation using 100 basis fiinctions, both of the electrons can be assigned to any of the % obtained m the calculation, resulting in 10,000 two-electron wavefimctions. For water, which has ten electrons, the number of electronic wavefiinctions with equal numbers of a and p spin electrons that can be constructed from 100 single-particle wavefimctions is roughly... [Pg.34]

Chemisorption occurs when the attractive potential well is large so that upon adsorption a strong chemical bond to a surface is fonued. Chemisorption involves changes to both the molecule and surface electronic states. For example, when oxygen adsorbs onto a metal surface, a partially ionic bond is created as charge transfers from the substrate to the oxygen atom. Other chemisorbed species interact in a more covalent maimer by sharing electrons, but this still involves perturbations to the electronic system. [Pg.294]

The so-called Flohenberg-Kolm [ ] theorem states that the ground-state electron density p(r) describing an A-electron system uniquely detemiines tlie potential V(r) in the Flamiltonian... [Pg.2179]

More advanced teclmiques take into account quasiparticle corrections to the DFT-LDA eigenvalues. Quasiparticles are a way of conceptualizing the elementary excitations in electronic systems. They can be detennined in band stmcture calculations that properly include the effects of exchange and correlation. In the... [Pg.2208]

The pseudopotential is derived from an all-electron SIC-LDA atomic potential. The relaxation correction takes into account the relaxation of the electronic system upon the excitation of an electron [44]- The authors speculate that ... the ability of the SIRC potential to produce considerably better band structures than DFT-LDA may reflect an extra nonlocality in the SIRC pseudopotential, related to the nonlocality or orbital dependence in the SIC all-electron potential. In addition, it may mimic some of the energy and the non-local space dependence of the self-energy operator occurring in the GW approximation of the electronic many body problem [45]. [Pg.2209]

QMC teclmiques provide highly accurate calculations of many-electron systems. In variational QMC (VMC) [112, 113 and 114], the total energy of the many-electron system is calculated as the expectation value of the Hamiltonian. Parameters in a trial wavefiinction are optimized so as to find the lowest-energy state (modem... [Pg.2220]

Perdew J P and Zunger A 1981 Self-interaction correction to density-functional approximations for many-electron systems Phys. Rev. B 23 5048... [Pg.2230]

The most important classes of functionalized [60]fullerene derivatives, e.g. methanofullerenes [341, pyrrolidinofullerenes [35], Diels-Alder adducts [34i] and aziridinofullerene [36], all give rise to a cancellation of the fivefold degeneration of their HOMO and tlireefold degeneration of their LUMO levels (figure Cl.2.5). This stems in a first order approximation from a perturbation of the fullerene s 7i-electron system in combination with a partial loss of the delocalization. [Pg.2413]

However, this procedure depends on the existence of the matrix G(R) (or of any pure gauge) that predicates the expansion in Eq. (90) for a full electronic set. Operationally, this means the preselection of a full electionic set in Eq. (129). When the preselection is only to a partial, truncated electronic set, then the relaxation to the truncated nuclear set in Eq. (128) will not be complete. Instead, the now tmncated set in Eq. (128) will be subject to a YM force F. It is not our concern to fully describe the dynamics of the truncated set under a YM field, except to say (as we have already done above) that it is the expression of the residual interaction of the electronic system on the nuclear motion. [Pg.157]

Figure 1. Jacobi vectors for a three-nuclei, four-electron system. The nuclei are Pi, P2, P3, and the electrons are ei, 02, 63, 64,... |

The H4 system is the prototype for many four-elecbon reactions [34]. The basic tetrahedral sfructure of the conical intersection is preserved in all four-electron systems. It arises from the fact that the four electrons are contributed by four different atoms. Obviously, the tefrahedron is in general not a perfect one. This result was found computationally for many systems (see, e.g., [37]). Robb and co-workers [38] showed that the structure shown (a tetraradicaloid conical intersection) was found for many different photochemical transformations. Having the form of a tetrahedron, the conical intersection can exist in two enantiomeric structures. However, this feature is important only when chiral reactions are discussed. [Pg.340]

We term the in-phase combination an aromatic transition state (ATS) and the out-of-phase combination an antiaromatic transition state (AATS). An ATS is obtained when an odd number of electron pairs are re-paired in the reaction, and an AATS, when an even number is re-paired. In the context of reactions, a system in which an odd number of electrons (3, 5,...) are exchanged is treated in the same way—one of the electron pairs may contain a single electron. Thus, a three-electron system reacts as a four-electron one, a five-electron system as a six-electron one, and so on. [Pg.346]

Electi ocyclic reactions are examples of cases where ic-electiDn bonds transform to sigma ones [32,49,55]. A prototype is the cyclization of butadiene to cyclobutene (Fig. 8, lower panel). In this four electron system, phase inversion occurs if no new nodes are fomred along the reaction coordinate. Therefore, when the ring closure is disrotatory, the system is Hiickel type, and the reaction a phase-inverting one. If, however, the motion is conrotatory, a new node is formed along the reaction coordinate just as in the HCl + H system. The reaction is now Mdbius type, and phase preserving. This result, which is in line with the Woodward-Hoffmann rules and with Zimmerman s Mdbius-Huckel model [20], was obtained without consideration of nuclear symmetry. This conclusion was previously reached by Goddard [22,39]. [Pg.347]

For odd electron systems in the absence of spatial symmehy H Eq. (12) becomes... [Pg.456]

potential curves for the A A electronic system of NH2 [25], Full... [Pg.499]

See also in sourсe #XX -- [ Pg.172 , Pg.173 , Pg.174 , Pg.175 , Pg.176 , Pg.177 , Pg.178 , Pg.179 ]

© 2019 chempedia.info