We examine the representation of solvent effects by continuum models in the frame of the Reaction Field Theory. Particular attention is devoted to the problem raised by the adaptation of the current methods of Quantum Chemistry in the Self Consistent Field approximation especially at a semiempirical level.A critical examination of the literature in the field shows that, for the main part, the proposed methods suffer from theoretical internal incoherence.As an illustration of this study, we propose an extension of the generalized Born formula which is able to account for the desolvation effects produced by the specific neighborhood of each center of the solvated species.
AbstractsI t is shown that any expectation value of any observable associated with a molecule is the sum of loge contributions and of loge pair contributions. This result provides a rigorous theoretical basis for the study of additive properties of molecules.I t is demonstrated that molecular wave functions (exact or approximate) can be expressed as a sum of functions corresponding to the various electronic events. Furthermore any of these event functions can be expressed in terms of correlated loge functions. This expression suggests many kinds of variational procedures of calculating wave functions (known methods and new ones).The case in which noncorrelated completely localized loge functions are used is discussed. If continuous functions are used the variational equation reduces to a sum of independent variational equations, each one corresponding to a particular electronic event. This is not so when discontinuous functions are used or when a delocalized function is added to replace the correlation interloge function.The noncorrelated completely localized loge model is analyzed in more detail. I t is seen that local spin operators can be introduced and that each event density operator is the product of the loge density operators. Therefore that model is an independent loge model. The corresponding generalized self-consistent field equations are derived. This treatment helps us to understand how a localized state of a molecule can produce an ion containing a deIocalized region, a phenomenon which is sometimes at the origin of some misunderstanding in photoelectron spectroscopy. Finally it is seen how virtual loge functions can be introduced to describe excited states. I1 est dtmontrt que chaque valeur moyenne d'un observable associt B une moltcule est la somme de contributions de loges et de paires de loges. Ce rtsultat fournit une base thtorique rigoureuse pour l'ttude des proprittts additives des moltcules. I1 est dtmontrk, que les fonctions d'onde moltculaires (exactes ou approchtes) peuvent itre exprimtes comme une somme de fonctions qui correspondent aux tvhements
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