Dimers theory

Newton MD, Kestner NR (1983) The water dimer theory versus experiment. Chem Phys Lett 94 198 - 201... 

Mooij, G. C. and Frenkel, D., Numerical test of the generalized Flory and generalized Flory dimer theories. J. Chem. Phys. 100, 6088-6091 (1994). 

By generalizing Flory s dimer theory. Hall and coworkers [22, 23] obtained the GF-D equation of state, which is as follows ... 

M. D. Newton and N. R. Kestner, Chem. Phys. Lett., 94,198(1983). The Water Dimer Theory Versus Experiment. 

Another popular approach is that of Hall and coworkers, who have attempted to extend the Flory-Huggins ideas to off-lattice polymer solutions, yielding first the Generalized Flory and then the Generalized Flory Dimer theories [214, 215]. The GFD theory provides a simple and tractable equation of state and produces rather accurate results for hard sphere chains. The drawback of this approach is that there is no unique way to extend it to more complicated cases, such as mixtures of polymer + solvent [216], heteropolymers [217], systems with attractive interactions [218] and it is difficult to include chemical details in a straightforward manner [212, 219, 220]. 

Miller, D. M., 1966, A re-examination of Stein s dimer theory of sugar transport in human erythrocytes, Biochim. Biophys. Acta 120 156. 

The "chemical" theory postulates that there is a dimerization equilibrium of the type... 

Two additional illustrations are given in Figures 6 and 7 which show fugacity coefficients for two binary systems along the vapor-liquid saturation curve at a total pressure of 1 atm. These results are based on the chemical theory of vapor-phase imperfection and on experimental vapor-liquid equilibrium data for the binary systems. In the system formic acid (1) - acetic acid (2), <() (for y = 1) is lower than formic acid at 100.5°C has a stronger tendency to dimerize than does acetic acid at 118.2°C. Since strong dimerization occurs between all three possible pairs, (fij and not... 

Enthalpies are referred to the ideal vapor. The enthalpy of the real vapor is found from zero-pressure heat capacities and from the virial equation of state for non-associated species or, for vapors containing highly dimerized vapors (e.g. organic acids), from the chemical theory of vapor imperfections, as discussed in Chapter 3. For pure components, liquid-phase enthalpies (relative to the ideal vapor) are found from differentiation of the zero-pressure standard-state fugacities these, in turn, are determined from vapor-pressure data, from vapor-phase corrections and liquid-phase densities. If good experimental data are used to determine the standard-state fugacity, the derivative gives enthalpies of liquids to nearly the same precision as that obtained with calorimetric data, and provides reliable heats of vaporization. 

VPLQFT is a computer program for correlating binary vapor-liquid equilibrium (VLE) data at low to moderate pressures. For such binary mixtures, the truncated virial equation of state is used to correct for vapor-phase nonidealities, except for mixtures containing organic acids where the "chemical" theory is used. The Hayden-0 Connell (1975) correlation gives either the second virial coefficients or the dimerization equilibrium constants, as required. 

A fiirther diflfieulty arises beeause the exaet wavefiinetions of the isolated moleeules are not known, exeept for one-eleetron systems. A eoimnon starting point is the Hartree-Foek wavefiinetions of the individual moleeules. It is then neeessary to inelude the eflfeets of intramoleeular eleetron eorrelation by eonsidering them as additional perturbations. Jeziorski and eoworkers [M] have developed and eomputationally implemented a triple perturbation theory of the syimnetry-adapted type. They have applied their method, dubbed SAPT, to many interaetions with more sueeess than might have been expeeted given the fiindamental doubts raised about the method. SAPT is eurrently both usefiil and praetieal. A reeent applieation [ ] to the CO2 dimer is illustrative of what ean be aehieved widi SAPT, and a rieh soiiree of referenees to previous SAPT work. 

Bukowski R, Sadie] J, Jeziorski B, Jankowski P, Szalewicz K, Kucharski S A, Williams H L and Rice B M 1999 Intermolecular potential of carbon dioxide dimer from symmetry-adapted perturbation theory J. Chem. Phys. 110 3785... 

The interaction between ions of the same sign is assumed to be a pure hard sphere repulsion for r < a. It follows from simple steric considerations that an exact solution will predict dimerization only if i < a/2, but polymerization may occur for o/2 < L = o. However, an approximate solution may not reveal the fiill extent of polymerization that occurs in a more accurate or exact theory. Cummings and Stell [ ] used the model to study chemical association of uncharged atoms. It is closely related to the model for adliesive hard spheres studied by Baxter [70]. 

An estimate of the enthalpy change which conesponds to the activation energy of the collision theory analysis of 167kJmoP may be made by assuming that the formation of tire dimer from two molecules of the monomer is energetically equivalent to tire dipole-dipole and dispersion interactions of two HI molecules. These exothermic sources of interaction are counterbalanced... 

The S domains form the viral shell by tight interactions in a manner predicted by the Caspar and Klug theory and shown in Figure 16.8. The P domains interact pairwise across the twofold axes and form protrusions on the surface. There are 30 twofold axes with icosahedral symmetry that relate the P domains of C subunits (green) and in addition 60 pseudotwofold axes relating the A (red) and B (blue) subunits (Figure 16.9). By this arrangement the 180 P domains form 90 dimeric protrusions. 

The behavior of assoeiating fluid near the hard wall was extensively studied in the framework of the theory diseussed above. The model of Cummings and Stell was applied to relatively dense fluids at a high degree of dimerization [33,36]. Fig. 1 presents the density profiles ealeulated within the framework of the eombined PYl/EMSA theory (i.e., the density profiles were evaluated from the PY 1 equation, whereas the bulk direet eorrelation fune-tions follow from the EMSA equation) and HNCl/EMSA approximations [33]. The ealeulations were performed for L = 0.42[Pg.181]

To illustrate this theory, we consider a one-component fluid with the interaction between the same species given by Eq. (36). Obviously, the model differs from that described in Sec. (II Bl). In particular, the geometrical constraints, which determine the type of association products in the case of a two-component model, are no longer valid. If we restrict ourselves to the case L < cr/2, only dimers and -mers built up of rigid, regular polygons are possible. 

The main conclusion which can be drawn from the results presented above is that dimerization of particles in a Lennard-Jones fluid leads to a stronger depletion of the proflles close to the wall, compared to a nonassociating fluid. On the basis of the calculations performed so far, it is difficult to conclude whether the second-order theory provides a correct description of the drying transition. An unequivocal solution of this problem would require massive calculations, including computer simulations. Also, it would be necessary to obtain an accurate equation of state for the bulk fluid. These problems are the subject of our studies at present. 

Eq. (101) is the multidensity Ornstein-Zernike equation for the bulk, one-component dimerizing fluid. Eqs. (102) and (103) are the associative analog of the singlet equation (31). The last equation of the set, Eq. (104), describes the correlations between two giant particles and may be important for theories of colloid dispersions. The partial correlation functions yield three... 

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