The MD results of Perera et al [187] show that the non-additive terms included in the potential of Caldwell et al [94] lead to significant difference with the results obtained with effective potentials, as to bond energy and cluster structure, especially for C1 . [Pg.407]

The effect of the three-body repulsive term ion-w-w has been clearly shown in a MD simulation of Cl in POL water [114]. Inclusion of this non-additive term reduces the hydration number from 7.1 to 6.1. While the former is close to the value calculated with the OPLS effective potential [197], the latter is in... [Pg.407]

Non-additive terms effects of polarization in the potential function. Polarization effects induced by the ionic presence on the ion-molecule system have been investigated. We use the expression by Lybrand and Kollman24 that includes in the potential function a self-consistent field (SCF) polarization energy Upoi based on classical electrostatics, given by ... [Pg.450]

This situation, despite the fact that reliability is increasing, is very undesirable. A considerable effort will be needed to revise the shape of the potential functions such that transferability is greatly enhanced and the number of atom types can be reduced. After all, there is only one type of carbon it has mass 12 and charge 6 and that is all that matters. What is obviously most needed is to incorporate essential many-body interactions in a proper way. In all present non-polarisable force fields many-body interactions are incorporated in an average way into pair-additive terms. In general, errors in one term are compensated by parameter adjustments in other terms, and the resulting force field is only valid for a limited range of environments. [Pg.8]

These quantities can be used to rearrange the equation for the EMF of a cell in non-aqueous medium into the form of a difference between the electrode potentials on the hydrogen scale for aqueous solutions with additional terms. [Pg.199]

Equations (37)—(39), where the non-additivity of multiple substituent effects is described by a cross-term, express correctly the rate data for bromination and other reactions of polysubstituted substrates. The question arises, therefore has the interaction constant, q, any physicochemical meaning in terms of mechanism and transition state charge To reply to this question, selectivity relationships (42) that relate the p-variation to the reactivity change and not to any substituent constant, have been considered (Ruasse et al., 1984). [Pg.260]

In the case that the chemical reaction proceeds much faster than the diffusion of educts to the surface and into the pore system a starvation with regard to the mass transport of the educt is the result, diffusion through the surface layer and the pore system then become the rate limiting steps for the catalytic conversion. They generally lead to a different result in the activity compared to the catalytic materials measured under non-diffusion-limited conditions. Before solutions for overcoming this phenomenon are presented, two more additional terms shall be introduced the Thiele modulus and the effectiveness factor. [Pg.392]

For higher-order reactions, the fluid-element concentrations no longer obey (1.9). Additional terms must be added to (1.9) in order to account for micromixing (i.e., local fluid-element interactions due to molecular diffusion). For the poorly micromixed PFR and the poorly micromixed CSTR, extensions of (1.9) can be employed with (1.14) to predict the outlet concentrations in the framework of RTD theory. For non-ideal reactors, extensions of RTD theory to model micromixing have been proposed in the CRE literature. (We will review some of these micromixing models below.) However, due to the non-uniqueness between a fluid element s concentrations and its age, micromixing models based on RTD theory are generally ad hoc and difficult to validate experimentally. [Pg.29]

The theory of interval observers first introduced by Rapaport et ai, [35], [55], establishes that, a necessary condition for designing such interval observers is that a known-inputs observer exists i.e., any observer that can be derived if b t) is known). If such an observer exists and if b t) is unknown i.e., only lower and upper bounds are known), the structure of this observer may be used to build an interval observer. In this section, this first requirement is cover by choosing an asymptotic observer as a basis for the interval structure. Indeed, in addition to be a known-inputs observer, the asymptotic observer has the property to be robust in the face of uncertainties on nonlinearities i.e., it permits the exact cancellation of the non-linear terms). [Pg.143]

In addition to fragment and graph indexing of polymer information, the POLID-CAS YR system also makes use of two distinct vocabularies for non-structural terms. The first vocabulary is, in essence, a controlled vocabulary of hierarchically ordered terms (taxonomy), supplemented by a second, more fluid vocabulary, which is subject to constant editing. The latter is used to further enhance the controlled vocabulary, e.g., the term isomerization , which is part of the controlled vocabulary, could be defined further by the terms racemization , tautomerization or rotation isomerization . Annotation of this kind is only a short step away from techniques, which we now associate with the terms tagging and folksonomies and which are typical components of Web 2.0 systems. POLIDCASYR s controlled vocabulary is structured according to a number of semantic categories such... [Pg.115]

Additional non-bonded terms may be included to account explicitly for such interactions as hydrogen bonding. [Pg.57]

The modeling of real immobilized-enzyme column reactors, mainly the fluidized-bed type, has been described (Emeiy and Cardoso, 1978 Allen, Charles and Coughlin, 1979 Kobayashi and Moo-Young, 1971) by mathematical models based on the dispersion concept (Levenspiel, 1972), by incorporation of an additional term to account for back-mixing in the ideal plug-flow reactor. This term describes the non-ideal effects in terms of a dispersion coefficient. [Pg.432]

The arguments are reviewed by Kaveh and Wiser (1984). They also describe observations of T2 behaviour in alkali and noble metals and—a point relevant to this book—the application to non-crystalline materials and other materials with short mean free path. They show that the time of relaxation t resulting from electron-electron scattering contains an additional term and is of the form... [Pg.73]

We can recognize the first term as the trace of the matrix for the well-stirred system of chapter 4 (let us call this tr(U)) multiplied by the positive quantity y. We have specified that we are to consider here systems which have a stable stationary state when well stirred, i.e. for which tr(U) is negative. The additional term associated with diffusion in eqn (10.47) can only make tr(J) more negative, apparently enhancing the stability. There are no Hopf bifurcations (where tr(J) = 0) induced by choosing a spatial perturbation with non-zero n. [Pg.273]

The e values for different solvent pairs can differ substantially because of additional terms -in Eq. (3.15), i.e. the value of s is non-universal. Any slight change in the interaction of units with the surface caused either by a change in the interaction in the mobile phase or a change in the water content of the adsorbent (see Sect. 4), changes e, but the form of the Kd(s — sab) function is approximately the same in different solvents. [Pg.155]

So far in this book we have only discussed non-relativistic Hamiltonian operators but when atomic or moleoular spectra are considered it is necessary to account for relativistic effects. These lead to additional terms in the Hamiltonian operator which can be related to the following phenomena ... [Pg.276]

As well as these additional terms there will also be changes to the Hamiltonian operator due to the relativistic change of electron mass with velocity. In ordinary optical spectroscopy the first two phenomena, (1) and (2), are the most important, leading to changes to the non-relativistic energy levels which are observable (effects (4) and (5) are important in n.m.r. and e.s.r. spectroscopy). [Pg.276]

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