Molecular Solutions

Aguilar M A and Olivares del Valle F J 1989 Solute-solvent interactions. A simple procedure for constructing the solvent capacity for retaining a molecular solute Ohem. Rhys. 129 439-50... 

We shall examine the simplest possible molecular orbital problem, calculation of the bond energy and bond length of the hydrogen molecule ion Hj. Although of no practical significance, is of theoretical importance because the complete quantum mechanical calculation of its bond energy can be canied out by both exact and approximate methods. This pemiits comparison of the exact quantum mechanical solution with the solution obtained by various approximate techniques so that a judgment can be made as to the efficacy of the approximate methods. Exact quantum mechanical calculations cannot be carried out on more complicated molecular systems, hence the importance of the one exact molecular solution we do have. We wish to have a three-way comparison i) exact theoretical, ii) experimental, and iii) approximate theoretical. 

One important class of integral equation theories is based on the reference interaction site model (RISM) proposed by Chandler [77]. These RISM theories have been used to smdy the confonnation of small peptides in liquid water [78-80]. However, the approach is not appropriate for large molecular solutes such as proteins and nucleic acids. Because RISM is based on a reduction to site-site, solute-solvent radially symmetrical distribution functions, there is a loss of infonnation about the tliree-dimensional spatial organization of the solvent density around a macromolecular solute of irregular shape. To circumvent this limitation, extensions of RISM-like theories for tliree-dimensional space (3d-RISM) have been proposed [81,82],... 

In studying the most familiar electrolytes, we have to deal with various molecular ions as well as atomic ions. The simplest molecular solute particle is a diatomic molecule that has roughly the same size and shape as two solvent particles in contact, and which goes into solution by occupying any two adjacent places that, in the pure solvent, are occupied by two adjacent solvent particles. This solution is formed by a process of substitution, but not by simple one-for-one substitution. There are two cases to discuss either the solute molecule is homonuclear, of-the type Bi, or it is heteronuclear, of the type BC. In either case let the number of solute molecules be denoted by nB, the number of solvent particles being nt. In the substitution process, each position occupied by a solvent particle is a possible position for one half of a solute molecule, and it is convenient to speak of each such position as a site, although in a liquid this site is, of course, not located at a fixed point in space. 

When an ionic solid such as NaCl dissolves in water the solution formed contains Na+ and Cl- ions. Since ions are charged particles, the solution conducts an electric current (Figure 2.12) and we say that NaCl is a strong electrolyte. In contrast, a water solution of sugar, which is a molecular solid, does not conduct electricity. Sugar and other molecular solutes are nonelectrolytes. 

Electrolyte solutions, which have ionic solutes, and nonclcctrolyte solutions, which have molecular solutes, were introduced in Section 1. 

J. G., De Lange, G. A. Molecular solutes in nematic liquid crystals orientational order and electric field gradients. Chem. Phys. Lett. 1983, 99, 271-274. 

Potential Distribution Methods and Free Energy Models of Molecular Solutions... 

Beck, T. L. Paulaitis, M. E. Pratt, L. R., The Potential Distribution Theorem and Models of Molecular Solutions, Cambridge University Press Cambridge, 2006... 

Molecular solutions, 8 697 Molecular speciation/quantification, infrared spectroscopy in, 23 140 Molecular spectroscopy, 10 508 Molecular structure. See also Chemical structures Molecular formulas of linear low density polyethylene, 20 182-184... 

An overview of these methods will be presented later in this Chapter. They will be introduced largely in the context of molecular solutes, although they can also be applied to ionic ones, as shall be discussed in a separate Section III.5. First, however, shall be summarized in some detail an approach that is less comprehensive than those that have been mentioned, but is readily applied and can be quite effective. 

In a very extensive test of the SM5 method (a type of GBM), Hawkins et al. found the average absolute deviation in AGsoivation to be 0.38 kcal/mole for 260 molecular solutes in water and in 90 organic solvents 131 for ions in water, it was 3.8 kcal/mole, for experimental AGsolvation between -58 and -110 kcal/mole. Semiempirical quantum-mechanical procedures were used. 

Table 13 gives the three contributions to AGhydration for five polyatomic ions, as computed by the PCM technique of Barone et al.,95 using their radii. As mentioned earlier, Gelectrostetic, Gcavitatlon and Gvdw are generally of the same order of magnitude for molecular solutes (Table 8) however this is not true for ionic ones, as can be seen in Table 13. Geiectrostatic is now often an order of magnitude larger.

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