Valence state effect

Sjeveral resolvable issues require attention before the QICAR approach has the same general usefulness as the QSAR approach. These issues include exploration of more explanatory variables, careful evaluation of ionic qualities used to calculate explanatory variables, examination of models capable of predicting effects for widely differing metals (e.g., metals of different valence states), effective inclusion of chemical specia-tion, examination of more effects, and assessment of the applicability of QICARs to phases such as sediment, soils, and foods. 

These valence state effects have been used to advantage in devising a procedure for the separation of neptunium, Np (Z = 93) from fission-product rare earths and yttrium and from uranium, U (Z = 92) and from plutonium, Pu (Z = 94) americium. Am (Z = 95) and curium. Cm (Z = 96). 

The first reliable energy band theories were based on a powerfiil approximation, call the pseudopotential approximation. Within this approximation, the all-electron potential corresponding to interaction of a valence electron with the iimer, core electrons and the nucleus is replaced by a pseudopotential. The pseudopotential reproduces only the properties of the outer electrons. There are rigorous theorems such as the Phillips-Kleinman cancellation theorem that can be used to justify the pseudopotential model [2, 3, 26]. The Phillips-Kleimnan cancellation theorem states that the orthogonality requirement of the valence states to the core states can be described by an effective repulsive... 

In the pseiidopotential construction, the atomic wavefrmctions for the valence electrons are taken to be nodeless. The pseiido-wavefrmction is taken to be identical to the appropriate all-electron wavefimction m the regions of interest for solid-state effects. For the core region, the wavefimction is extrapolated back to the... 

For this reason, there has been much work on empirical potentials suitable for use on a wide range of systems. These take a sensible functional form with parameters fitted to reproduce available data. Many different potentials, known as molecular mechanics (MM) potentials, have been developed for ground-state organic and biochemical systems [58-60], They have the advantages of simplicity, and are transferable between systems, but do suffer firom inaccuracies and rigidity—no reactions are possible. Schemes have been developed to correct for these deficiencies. The empirical valence bond (EVB) method of Warshel [61,62], and the molecular mechanics-valence bond (MMVB) of Bemardi et al. [63,64] try to extend MM to include excited-state effects and reactions. The MMVB Hamiltonian is parameterized against CASSCF calculations, and is thus particularly suited to photochemistry. 

In a combined experimental/computational study, the vibrational spectra of the N9H and N7H tautomers of the parent purine have been investigated [99SA(A) 2329]. Solvent effects were estimated by SCRF calculations. Vertical transitions, transition dipole moments, and permanent dipole moments of several low-lying valence states of 2-aminopurine 146 were computed using the CIS and CASSCF methods [98JPC(A)526, 00JPC(A)1930]. While the first excited state of adenine is characterized by an n n transition, it is the transition for 146. The... 

As was the case with lanthanide crystal spectra (25), we found that a systematic analysis could be developed by examining differences, AP, between experimentally-established actinide parameter values and those computed using Hartree-Fock methods with the inclusion of relativistic corrections (24), as illustrated in Table IV for An3+. Crystal-field effects were approximated based on selected published results. By forming tabulations similar to Table IV for 2+, 4+, 5+ and 6+ spectra, to the extent that any experimental data were available to test the predictions, we found that the AP-values for Pu3+ provided a good starting point for approximating the structure of plutonium spectra in other valence states. However,... 

For the spinel, Hercyanite, cissume that the cation changes in valence state. Then, draw a diagram illustrating the probable ion diffusion processes, give the diffusion conditions and the diffusion reactions, including the effect of induced crystal lattice defects. 

The C—S bond lengths vary upon changing carbon valence states. However, the sulfones and sulfoxides show less sensitivity to these changes than the analogous sulfides . These effects can be illustrated by considering the C—S bond lengths (A) in analogous dimethyl and diphenyl derivatives ... 

Effects of spacer groups on the formation and properties of the mixed-valence states of conjugated ferrocene dimers have been extensively studied by both electrochemical and spectroscopic methods. It should be noted that a characteristic feature in the electronic spectra of ferrocene dimers with conjugated spacer groups is the appearance of metal-to-ligand charge transfer (MLCT) bands in the neutral form as well as IT bands in the mixed-valence state. The dimer Fc — CH=CH — Fc... 

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