Generalized curve-crossing model

The latter is, except for a couple of terms related to solvent reorganization, the Marcus equation. It should be noted that such curve-crossing models have been used in connection with VB methods to rationalize chemical reactivity and selectivity in a more general sense. ... 

In Fig. 4.18, the influence of the kinetic parameters (k°, a) on the ADDPV curves is modeled at a spherical microelectrode l /Dr /r, = 0.2). In general terms, the peak currents decrease and the crossing and peak potentials shift toward more negative values as the electrode processes are more sluggish (see Fig. 4.18a). For quasireversible systems (k° 10-2 — 10 4 cm s ). the peak currents are very sensitive to the value of the heterogeneous rate constant (k°) whereas the variation of the crossing potential is less apparent. On the other hand, for totally irreversible... 

Apparent viscosity-shear rate data of food polymer dispersions have been reviewed by Launay et al. (1986), Lopes da Silva and Rao (1992) and others. The general log versus log y curve, discussed in Chapter 2, has been used to characterize food polymer dispersions. For example, Lopes da Silva et al. (1992) found that both the modified Carreau and the Cross models, wherein the infinite shear viscosity was considered to be negligible, described the apparent viscosity-shear rate data of locustbean (LB)... 

S. S. Shaik and P. C. Hiberty, Curve crossing diagrams as general models for chemical reactivity and structure, Theoretical Models of Chemical Bonding. Part 4 (Z. B. Maksic, ed.), Springer-Verlag, Berlin, 1991, p. 269. 

We refer to Chapter 4 for a detailed discussion on the definition and explicit construction of diabatic states. The diabatic representation is generally advantageous for the computational treatment of the nuclear dynamics if the adiabatic potential-energy surfaces exhibit degeneracies such as conical intersections. Moreover, the diabatic representation often reflects more clearly than the Born ppenheimer adiabatic representation the essential physics of curve crossing problems and is thus very useful for the construction of appropriate model Hamiltonians for polyatomic systems. 

Curve Crossing Diagrams as General Models for Chemical Reactivity and Structure... 

---