Localized charge

Minimal END has also been applied to a model system for intramolecular electron transfer. The small triatomic system LiHLi is bent C2v structure. But the linear structure presents an unrestricted Haiti ee-Fock (TJHF) broken symmetry solution with the two charge localized stmctures... 

Ollis and Ramsden state that A compound may be appropriately called mesoionic if it is a five-membered heterocycle which cannot be represented satisfactorily by any one covalent or polar structure and possesses a sextet of electrons in association with the five atoms comprising the ring . From the point of view of systematic nomenclature, compounds of this type are difficult to deal with, since most available nomenclature systems are designed so as to name one particular bond- and charge-localized canonical form. 

Aicoholate anions have negative charge localized on a single oxygen. 

A vanety of oxo-bridged dicationic Inflates with the positive charges localized on the heteroatoms can be prepared from tnflic anhydride and the corresponding substrates [90, 91, 92, 93], Treatment of hexamethylphosphonctriamide with tnflic anhydnde yields the diphosphonium inflate salt [90] (equation 42). 

Compare atomic charges and electrostatic potential maps for the three cations. For each, is the charge localized or delocalized Is it associated with an empty a-type or Tt-type orbital Examine the lowest-unoccupied molecular orbital (LUMO) of each cation. Draw all of the resonance contributors needed for a complete description of each cation. Assign the hybridization of the C" atom, and describe how each orbital on this atom is utilized (o bond, n bond, empty). How do you explain the benzene ring effects that you observe ... 

A comparative study on ylide stability as a function of the heteroatom type was carried out by Doering et al. [3,4]. They concluded that the phosphorus and sulfur ylides are the most stable ones. The participation of three-dimensional orbitals in the covalency determines the resonance stabilization of the phosphorus and sulfur ylides [5-8]. The nitrogen ylides are less stable from this point of view. The only stabilization factor involves electrostatic interactions between the two charges localized on adjacent nitrogen and carbon atoms [9]. 

Active Figure 20.1 An alkoxide ion has its charge localized on one oxygen atom and is less stable, while a carboxylate ion has the charge spread equally over both oxygens and is therefore more stable. Sign in at www.thomsonedu.com ro see a simulation based on this figure and to take a short quiz. 

Besides its temperature dependence, hopping transport is also characterized by an electric field-dependent mobility. This dependence becomes measurable at high field (namely, for a field in excess of ca. 10d V/cm). Such a behavior was first reported in 1970 in polyvinylcarbazole (PVK) [48. The phenomenon was explained through a Poole-ITenkel mechanism [49], in which the Coulomb potential near a charged localized level is modified by the applied field in such a way that the tunnel transfer rale between sites increases. The general dependence of the mobility is then given by Eq. (14.69)... 

Scheme 5 Electronic structures of TTF salts, showing charge localization into uniform chains or dicationic dimers in the TTF+ X salts (left) or the partially filled conduction bands in mixed-valence (TTF X salts (right)...

Olsen S, Lamothe K, MartiAAnez TJ (2010) Protonic gating of excited-state twisting and charge localization in GFP chromophores a mechanistic hypothesis for reversible photoswitching. J Am Chem Soc 132 1192-1193... 

NH3 has substantial negative charge localized in the region of its nonbonding electron pair. 

The overall conclusion from the reaction of BP and 6-substituted BP radical cations with nucleophiles of various strengths is that weak nucleophiles display higher selectivity toward the position of highest charge localization. Thus another important factor in the chemical reactivity of radical cations is represented by the strength of the nucleophile. 

Ionization Potential of PAH and Charge Localization in Radical Cations... 

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