Charge distribution creating

Debye postulated that close approach of molecules mutually distorts their charge distributions, creating induced dipoles that reduce repulsion and increase attraction between them. The result is the apparent slight reduction in pressure due to stickiness van der Waals attractions) of these brief molecular collisions. 

The energies of the FE components may serve as a measure of the density of the charge distributions created on the fracture surface. 

There is an interesting consequence of the presence ofthe nonadiabatic frequency in these equations. It is possible that is negative. As in dielectrics, a charge distribution creates its own well, and the frequency of this well may be larger than the barrier frequency. Rather than at the top of a barrier, the particle then finds itself in a well. If the solvent is very slow to adjust, that is, for high solvent friction, it can take quite some time for the solvent to react and relax. Such a situation is depicted in Figure 9.7. 

The third term in Equation (11.52) is the correction factor corresponding to the work done creating the charge distribution of the solute within the cavity in the dielectric medium. the gas-phase wavefimction. 

To calculate AGgi c, we must take account of the work done in creating the charge distribi w ithin the cavity in the dielectric medium. This is equal to one-half of the electrostatic i action energy between the solute charge distribution and the polarised dielectric, amd S ... 

There are two general cases of dipole-dipole forces those between molecules in which the distribution of electronic charge is centrosymmetric and those in which it is not. In the first case, there are no permanent electrical dipoles, whereas there is a permanent dipole if the charge distribution is non-centro-symmetric. When permanent dipoles are not present, there are nevertheless fluctuating dipoles as a result of atomic vibrations. These are always present because of zero-point motion. At temperatures greater than 0°K, thermal energy further excites the molecular vibrational modes which create fluctuating electric dipoles. 

Within this framework, the effect of the ligand can be described by an operator UCY, which is the sum of one-electron operators for all the 4P electrons of the lanthanide, which accounts for the potential created by a charge distribution p(R)... 

In order to avoid overparametrization, we can use the point charge electrostatic model (PCE model) [19, 20], in which N ligands are represented by their point charges (Zt). The Hcf generated by a charge distribution can be written in its most primitive form as a sum of Coulomb fields created by the charges. The Aq CF parameters can then be calculated by the following expression ... 

For polarizable charge distributions, additional classical-type interactions arise from the induced dipole, quadrupole, and higher moments on each monomer, which are proportional to the fields created by the asymmetric charge distribution on the other monomer. The proportionality constants for each multipole field are the monomer polarizabilities aa and ah (a111 for dipole fields, a(Q) for quadrupole fields, etc.). The leading two induction interactions are ... 

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