Finite-sized

Boyle s law At constant temperature the volume of a given mass of gas is inversely proportional to the pressure. Although exact at low pressures, the law is not accurately obeyed at high pressures because of the finite size of molecules and the existence of intermolecular forces. See van der Waals equation. 

In the previous sections we have described the interaction of the electromagnetic field with matter, that is, tlie way the material is affected by the presence of the field. But there is a second, reciprocal perspective the excitation of the material by the electromagnetic field generates a dipole (polarization) where none existed previously. Over a sample of finite size this dipole is macroscopic, and serves as a new source tenu in Maxwell s equations. For weak fields, the source tenu, P, is linear in the field strength. Thus,... 

At concentrations greater than 0.001 mol kg equation A2.4.61 becomes progressively less and less accurate, particularly for imsynnnetrical electrolytes. It is also clear, from table A2.4.3. that even the properties of electrolytes of tire same charge type are no longer independent of the chemical identity of tlie electrolyte itself, and our neglect of the factor in the derivation of A2.4.61 is also not valid. As indicated above, a partial improvement in the DH theory may be made by including the effect of finite size of the central ion alone. This leads to the expression... 

If the finite size of the system is ignored (after all, A is probably 10 or greater), the compressibility is essentially infinite at the critical point, and then so are the fluctuations. In reality, however, the compressibility diverges more sharply than classical theory allows (the exponent y is significantly greater dian 1), and thus so do the fluctuations. 

A system of interest may be macroscopically homogeneous or inliomogeneous. The inliomogeneity may arise on account of interfaces between coexisting phases in a system or due to the system s finite size and proximity to its external surface. Near the surfaces and interfaces, the system s translational synnnetry is broken this has important consequences. The spatial structure of an inliomogeneous system is its average equilibrium property and has to be incorporated in the overall theoretical stnicture, in order to study spatio-temporal correlations due to themial fluctuations around an inliomogeneous spatial profile. This is also illustrated in section A3.3.2. 

A schematic diagram of a simple TOP instrument is shown in figure B 1.7.17(a). Since the ion source region of any instrument has a finite size, the ions will spend a certain amount of time in the source while they are accelerating. If the... 

Kent PRC, Flood R Q, Williamson A J, Needs R J, Foulkes W M C and Ra]agopal G 1999 Finite-size errors in quantum many-body simulations of extended systems Phys. Rev. B 59 1917-29... 

Both MD and MC teclmiques evolve a finite-sized molecular configuration forward in time, in a step-by-step fashion. (In this context, MC simulation time has to be interpreted liberally, but there is a broad coimection between real time and simulation time (see [1, chapter 2]).) Connnon features of MD and MC simulation teclmiques are that there are limits on the typical timescales and length scales that can be investigated. The consequences of finite size must be considered both in specifying the molecular mteractions, and in analysing the results. 

Near critical points, special care must be taken, because the inequality L will almost certainly not be satisfied also, cridcal slowing down will be observed. In these circumstances a quantitative investigation of finite size effects and correlation times, with some consideration of the appropriate scaling laws, must be undertaken. Examples of this will be seen later one of the most encouraging developments of recent years has been the establishment of reliable and systematic methods of studying critical phenomena by simulation. 

Flere we discuss the exploration of phase diagrams, and the location of phase transitions. See also [128. 129. 130. 131] and [22, chapters 8-14]. Very roughly we classify phase transitions into two types first-order and continuous. The fact that we are dealing with a finite-sized system must be borne in mind, in either case. 

For both first-order and continuous phase transitions, finite size shifts the transition and rounds it in some way. The shift for first-order transitions arises, crudely, because the chemical potential, like most other properties, has a finite-size correction p(A)-p(oo) C (l/A). An approximate expression for this was derived by Siepmann et al [134]. Therefore, the line of intersection of two chemical potential surfaces Pj(T,P) and pjj T,P) will shift, in general, by an amount 0 IN). The rounding is expected because the partition fiinction only has singularities (and hence produces discontinuous or divergent properties) in tlie limit i—>oo otherwise, it is analytic, so for finite Vthe discontinuities must be smoothed out in some way. The shift for continuous transitions arises because the transition happens when L for the finite system, but when i oo m the infinite system. The rounding happens for the same reason as it does for first-order phase transitions whatever the nature of the divergence in thennodynamic properties (described, typically, by critical exponents) it will be limited by the finite size of the system. 

Privman V (ed) 1990 Finite Size Scaiing and Numericai Simuiation of Statisticai Systems (Singapore World Scientific)... 

Siepmann J I, McDonald I R and Frenkel D 1992 Finite-size corrections to the chemical potential J. Phys. Oondens. Matter 4 679-91... 

Cardy J L (ed) Finite-Size Scaiing vol 2 Ourrent Physics—Sources and Oomments (Amsterdam North-Holland)... 

Binder K 1981 Finite size scaling analysis of Ising-model block distribution-functions Z. Phys. B. Oondens. Matter. 43 119-40... 

Challa MSS, Landau D P and Binder K 1986 Finite-size effects at temperature-driven Ist-order transitions Phys. Rev. B 34 1841 -52... 

Binder K and Landau D P 1984 Finite size scaling at Ist-order phase transitions Phys. Rev. B 30 1477-85... 

Deutsoh H-P and Binder K 1993 Mean-field to Ising orossover in the oritioal behavior of polymer mixtures—a finite size sealing analysis of Monte Carlo simulations J. Physique II 3 1049... 

The ultimate reason for studying water clusters is of course to understand tire interactions in bulk water (tliough clusters are interesting in tlieir own right, too, because finite-size systems can have special properties). There has been... 

The form factor f takes the directional dependence of scattering horn a spherical body of finite size into account. The reciprocal distance s depends on the scattering angle and the wavelength A as given by Eq. (23). 

When a model is based on a picture of an interconnected network of pores of finite size, the question arises whether it may be assumed that the composition of the gas in the pores can be represented adequately by a smooth function of position in the medium. This is always true in the dusty gas model, where the solid material is regarded as dispersed on a molecular scale in the gas, but Is by no means necessarily so when the pores are pictured more realistically, and may be long compared with gaseous mean free paths. To see this, consider a reactive catalyst pellet with Long non-branching pores. The composition at a point within a given pore is... 

To develop this model into a quantitative relationship between T j, and the thickness of the crystal, we begin by realizing that for the transition crystal liquid, AG is the sum of two contributions. One of these is AG , which applies to the case of a crystal of infinite (superscript °o) size the other AG arises specifically from surface (superscript s) effects which reflect the finite size of the crystal ... 

The starting point for obtaining quantitative descriptions of flow phenomena is Newton s second law, which states that the vector sum of forces acting on a body equals the rate of change of momentum of the body. This force balance can be made in many different ways. It may be appHed over a body of finite size or over each infinitesimal portion of the body. It may be utilized in a coordinate system moving with the body (the so-called Lagrangian viewpoint) or in a fixed coordinate system (the Eulerian viewpoint). Described herein is derivation of the equations of motion from the Eulerian viewpoint using the Cartesian coordinate system. The equations in other coordinate systems are described in standard references (1,2). 

Macroscopic Equations An arbitraiy control volume of finite size is bounded by a surface of area with an outwardly directed unit normal vector n. The control volume is not necessarily fixed in space. Its boundary moves with velocity w. The fluid velocity is v. Figure 6-3 shows the arbitraiy control volume. 

This has also commonly heen termed direct interception and in conventional analysis would constitute a physical boundary condition path induced hy action of other forces. By itself it reflects deposition that might result with a hyj)othetical particle having finite size hut no fThis parameter is an alternative to N f, N i, or and is useful as a measure of the interactive effect of one of these on the other two. Schmidt numher. 

Eor instance, the contribution of water beyond 12 A from a singly charged ion is 13.7 kcal/mol to the solvation free energy or 27.3 kcal/mol to the solvation energy of that ion. The optimal treatment is to use Ewald sums, and the development of fast methods for biological systems is a valuable addition (see Chapter 4). However, proper account must be made for the finite size of the system in free energy calculations [48]. 

The discussion of diffraction so far has made no reference to the size of the 2D grating. It has been assumed that the grating is infinite. In analogy with optical or X-ray diffraction, finite sizes of the ordered regions on the surface (finite-sized gratings) broaden the diffracted beams. From an analysis of the diffracted-beam shapes, the types of structural disorder in the surface region can be identified and quantified. - ... 

Phase transitions in overlayers or surfaces. The structure of surface layers may undergo a transition with temperature or coverage. Observation of changes in the diffraction pattern gives a qualitative analysis of a phase transition. Measurement of the intensity and the shape of the profile gives a quantitative analysis of phase boundaries and the influence of finite sizes on the transition. ... 

Large deformation contacts and finite size effects... 

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