Other linear combinations of simple potentials are also widely used to mimic the interactions in real systems. An example is the following. [Pg.440]

Here =MkT. In a real system the thennal coupling with surroundings would happen at the surface in simulations we avoid surface effects by allowing this to occur homogeneously. The state of the surroundings defines the temperature T of the ensemble. [Pg.2246]

Information about critical points on the PES is useful in building up a picture of what is important in a particular reaction. In some cases, usually themially activated processes, it may even be enough to describe the mechanism behind a reaction. However, for many real systems dynamical effects will be important, and the MEP may be misleading. This is particularly true in non-adiabatic systems, where quantum mechanical effects play a large role. For example, the spread of energies in an excited wavepacket may mean that the system finds an intersection away from the minimum energy point, and crosses there. It is for this reason that molecular dynamics is also required for a full characterization of the system of interest. [Pg.254]

Worth and Cederbaum [100], propose to facilitate the search for finding a conical intersection if the two states have different symmetiies If they cross along a totally symmetric nuclear coordinate, then the crossing point is a conical intersection. Even this simplifying criterion leaves open a large number of possibilities in any real system. Therefore, Worth and Cederbaum base their search on large scale nuclear motions that have been identified experimentally to be important in the evolution of the system after photoexcitation. [Pg.385]

In this section, we concentrate on a few examples to show the degree of relevance of the theory presented in the previous sections. For this purpose, we analyze the conical intersections of two real two-state systems and one real system resembling a tri-state case. [Pg.699]

In order to compute average properties from a microscopic description of a real system. one must evaluate in tegrals over phase space. For an A -particle system in an cn sem hie with distribution... [Pg.96]

Forces between the particles in a real gas or liquid affect the virial, and thence the pressure. The total virial for a real system equals the sum of an ideal gas part (—3P V) and a contribution due to interactions between the particles. The result obtained is ... [Pg.323]

Each state of the extended system that is generated by the molecular dynamics simulatic corresponds to a unique state of the real system. There is not, however, a dire correspondence between the velocities and the time in the real and the extended system The velocities of the atoms in the real system are given by ... [Pg.401]

The value of the additional degree of freedom s can change and so the time step in real tin can fluctuate. Thus regular time intervals in the extended system correspond to a trajecto of the real system which is unevenly space in time. [Pg.401]

An individual point in phase space, denoted by F, corresponds to a particular geometry of all the molecules in the system. There are many points in this phase space that will never occur in any real system, such as configurations with two atoms in the same place. In order to describe a real system, it is necessary to determine what configurations could occur and the probability of their occurrence. [Pg.12]

Ideal Adsorbed Solution Theory. Perhaps the most successful approach to the prediction of multicomponent equiUbria from single-component isotherm data is ideal adsorbed solution theory (14). In essence, the theory is based on the assumption that the adsorbed phase is thermodynamically ideal in the sense that the equiUbrium pressure for each component is simply the product of its mole fraction in the adsorbed phase and the equihbrium pressure for the pure component at the same spreadingpressure. The theoretical basis for this assumption and the details of the calculations required to predict the mixture isotherm are given in standard texts on adsorption (7) as well as in the original paper (14). Whereas the theory has been shown to work well for several systems, notably for mixtures of hydrocarbons on carbon adsorbents, there are a number of systems which do not obey this model. Azeotrope formation and selectivity reversal, which are observed quite commonly in real systems, ate not consistent with an ideal adsorbed... [Pg.256]

decomposition rate of peroxide is thus increased, the consequent lowering of steady-state peroxide concentration leaves the effective rate unchanged in the simple peroxide cycle kinetic scheme (25). In real systems, at certain critical levels, a catalyst can become an inhibitor (2,180). [Pg.342]

Phase diagrams can be used to predict the reactions between refractories and various soHd, Hquid, and gaseous reactants. These diagrams are derived from phase equiHbria of relatively simple pure compounds. Real systems, however, are highly complex and may contain a large number of minor impurities that significantly affect equiHbria. Moreover, equiHbrium between the reacting phases in real refractory systems may not be reached in actual service conditions. In fact, the successful performance of a refractory may rely on the existence of nonequilibrium conditions, eg, environment (15—19). [Pg.27]

Inhibitors are often iacluded ia formulations to iacrease the pot life and cute temperature so that coatings or mol dings can be convenientiy prepared. An ideal sUicone addition cure may combine iastant cure at elevated temperature with infinite pot life at ambient conditions. Unfortunately, real systems always deviate from this ideal situation. A proposed mechanism for inhibitor (I) function is an equUibtium involving the inhibitor, catalyst ligands (L), the sUicone—hydride groups, and the sUicone vinyl groups (177). [Pg.48]

The relations between the compositions of Pordand cements and some other common hydrauhc cements are shown in the CaO—Si02—AI2O2 phase diagram of Figure 2 (5). In this diagram, Fe202 has been combined with AI2O2 to yield the Al O content used. This is a commonly appHed approximation that permits a two-dimensional representation of the real systems. [Pg.283]

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