By V. May, et. al.
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Extra resources for Charge and Energy Transfer Dynamics in Molec. Systs.
The long-range electrostatic interactions are, of course, not included in the supermolecule approach. They are, however, accounted for in the so-called continuum models, which are in turn applicable whenever short-range interactions are negligible. The model implies that we discard the discrete nature of the solvent and treat it as a homogeneous entity fully characterized by its macroscopic properties. This approach will be discussed in the following section. Indeed, it is ﬂexible enough to accommodate the supermolecule approach yielding a mixed description that may distinguish between the ﬁrst solvation shell and the rest of the solvent.
We note in caution that this section by no means presents a complete treatment of the ﬁeld of electronic structure theory. The intention is rather to provide a background for the following discussions. The reader interested in a more comprehensive overview of the state of the art is referred to the literature quoted at the end of this chapter. Let us start with the situation in which the Coulomb interaction between electrons is switched off. 11) becomes a P el sum of single-particle Hamiltonians, Hel (R) D Nj D1 h el (r j ), containing the kinetic energy of the jth electron and the Coulomb energy due to its interaction with the static nuclei.
The distance jx x s j should be large. term. An important exception occurs if the dipole moment vanishes for symmetry reasons. The dipole moment of the small volume element d s can of course be traced to the individual molecular dipole moments. 45) m2∆V(x s ) with Z dm D d3 x 0 x 0 m (x 0 ). 46) Apparently, whether a molecule has a permanent dipole moment or not is determined by its symmetry. Systems like CCl4 or diatomics like H2 or N2 do not have a permanent dipole; the dielectric is nonpolar.
Charge and Energy Transfer Dynamics in Molec. Systs. by V. May, et. al.