Charge/solvent interactions

Microscopic models aim at describing the charge-charge and charge-solvent interaction in full molecular detail, thus circrrmventing the use of a dielectric corrstant (Warshel and Rnssell, 1984 Russel and Warshel, 1985 van Belle et al, 1987). Although this may seem like the proper approach, practical limitations on computer capacity and speed make approximations unavoidable, especially in the solvent description. 

To take into account the charge-solvent interaction, we introduce a multidimensional coordinate Xk that characterizes the polarization of water molecules around the k-th base pair. Then a standard linear response expansion enables one to express the interaction with the water environment as a function of Xk as... 

B. A. Luty, M. E. Davis, and J. A. McCammon,/. Comput. Chem.,13, 768 (1992). Electrostatic Energy Calculations by a Finite-Difference Method Rapid Calculation of Charge-Solvent Interaction Energies. 

This fomuila does not include the charge-dipole interaction between reactants A and B. The correlation between measured rate constants in different solvents and their dielectric parameters in general is of a similar quality as illustrated for neutral reactants. This is not, however, due to the approximate nature of the Bom model itself which, in spite of its simplicity, leads to remarkably accurate values of ion solvation energies, if the ionic radii can be reliably estimated [15],... 

Specific solute-solvent interactions involving the first solvation shell only can be treated in detail by discrete solvent models. The various approaches like point charge models, siipennoleciilar calculations, quantum theories of reactions in solution, and their implementations in Monte Carlo methods and molecular dynamics simulations like the Car-Parrinello method are discussed elsewhere in this encyclopedia. Here only some points will be briefly mentioned that seem of relevance for later sections. 

The electrostatic free energy contribution in Eq. (14) may be expressed as a thennody-namic integration corresponding to a reversible process between two states of the system no solute-solvent electrostatic interactions (X = 0) and full electrostatic solute-solvent interactions (X = 1). The electrostatic free energy has a particularly simple form if the thermodynamic parameter X corresponds to a scaling of the solute charges, i.e., (X,... 

In a recent paper. Mo and Gao [5] used a sophisticated computational method [block-localized wave function energy decomposition (BLW-ED)] to decompose the total interaction energy between two prototypical ionic systems, acetate and meth-ylammonium ions, and water into permanent electrostatic (including Pauli exclusion), electronic polarization and charge-transfer contributions. Furthermore, the use of quantum mechanics also enabled them to account for the charge flow between the species involved in the interaction. Their calculations (Table 12.2) demonstrated that the permanent electrostatic interaction energy dominates solute-solvent interactions, as expected in the presence of ion species (76.1 and 84.6% for acetate and methylammonium ions, respectively) and showed the active involvement of solvent molecules in the interaction, even with a small but evident flow of electrons (Eig. 12.3). Evidently, by changing the solvent, different results could be obtained. 

In the Born equation, the ion solvent interaction energy is determined only by one physical parameter of the solvent, i.e., the dielectric constant. However, since actual ion-solvent interactions include specific interactions such as the charge-transfer interaction or hydrogen bonds, it is natural to think that the Born equation should be insufficient. It is well known that the difference in the behavior of an ion in different solvents is not often elucidated in terms of the dielectric constant. 

Solvatochromic pareuaeters, so called because they were Initially derived from solvent effects on UV/visible spectra, have been applied subsequently with success to a wide variety of solvent-dependent phenomena and have demonstrated good predictive ability. The B jo) scale of solvent polarity is based on the position of the intermolecular charge transfer absorption band of Reichardt s betaine dye [506]. Et(io> values are available for over 200 common solvents and have been used by Dorsey and co-%rarkers to study solvent interactions in reversed-phase liquid chromatography (section 4.5.4) [305,306]. For hydrogen-bonding solvents the... 

In fact, the orientation of water at the potential of zero charge is expected to depend approximately linearly on the electronegativity of the metal.9 This orientation (see below) may be deduced from analysis of the variation of the potential drop across the interface with surface charge for different metals and electrolytes. Such analysis leads to the establishment of a hydrophilicity scale of the metals ( solvophilicity for nonaqueous solvents) which expresses the relative strengths of metal-solvent interaction, as well as the relative reactivities of the different metals to oxygen.23... 

---