Distribution functions liquids

Figure A2.3.8 Atom-atom distribution functions liquid water at 25°C determined...

Terzis, A. F. and Samulski, E. T. (1996) Spatial distribution functions liquid CH3CN and C02, Chem, Phys. Lett. 251, 157-63. 

Another statistical mechanical approach makes use of the radial distribution function g(r), which gives the probability of finding a molecule at a distance r from a given one. This function may be obtained experimentally from x-ray or neutron scattering on a liquid or from computer simulation or statistical mechanical theories for model potential energies [56]. Kirkwood and Buff [38] showed that for a given potential function, U(r)... 

Unlike the solid state, the liquid state cannot be characterized by a static description. In a liquid, bonds break and refomi continuously as a fiinction of time. The quantum states in the liquid are similar to those in amorphous solids in the sense that the system is also disordered. The liquid state can be quantified only by considering some ensemble averaging and using statistical measures. For example, consider an elemental liquid. Just as for amorphous solids, one can ask what is the distribution of atoms at a given distance from a reference atom on average, i.e. the radial distribution function or the pair correlation function can also be defined for a liquid. In scattering experiments on liquids, a structure factor is measured. The radial distribution fiinction, g r), is related to the stnicture factor, S q), by... 

Typical results for a semiconducting liquid are illustrated in figure Al.3.29 where the experunental pair correlation and structure factors for silicon are presented. The radial distribution function shows a sharp first peak followed by oscillations. The structure in the radial distribution fiinction reflects some local ordering. The nature and degree of this order depends on the chemical nature of the liquid state. For example, semiconductor liquids are especially interesting in this sense as they are believed to retain covalent bonding characteristics even in the melt. 

Born M and Green H S 1946 A general kinetic theory of liquids I. The molecular distribution functions Proc. R. Soc. A 188 10... 

Typical shapes of the orientation distribution function are shown in figure C2.2.10. In a liquid crystal phase, the more highly oriented the phase, the moreyp tends to be sharjDly peaked near p=0. However, in the isotropic phase, a molecule has an equal probability of taking on any orientation and then/P is constant. 

Figure C2.2.10. Orientational distribution functions for (a) a highly oriented liquid crystal phase, (b) a less well...

Leadbetter A J and Norris E K 1979 Distribution functions in hree liquid crystals from x-ray diffraction measurements Moiec. Phys. 38 669-86... 

Fig. 6.2 Radial distribution function determined from a lOOps molecular dynamics simulation of liquid argon at a temperature of 100K and a density of 1.396gcm. ...

Idistribution functions can be measured experimentally using X-ray diffraction. The regular arrangement of the atoms in a crystal gives the characteristic X-ray diffraction pattern with bright, sharp spots. For liquids, the diffraction pattern has regions of high and low intensity but no sharp spots. The X-ray diffraction pattern can be analysed to calculate an experimental distribution function, which can then be compared with that obtained from the simulation. 

FIGURE 2.2 Radial distribution functions for (a) a hard sphere fluid, (A) a real gas, (c) a liquid, (li) a crystal. 

A very important aspect of both these methods is the means to obtain radial distribution functions. Radial distribution functions are the best description of liquid structure at the molecular level. This is because they reflect the statistical nature of liquids. Radial distribution functions also provide the interface between these simulations and statistical mechanics. 

One important class of integral equation theories is based on the reference interaction site model (RISM) proposed by Chandler [77]. These RISM theories have been used to smdy the confonnation of small peptides in liquid water [78-80]. However, the approach is not appropriate for large molecular solutes such as proteins and nucleic acids. Because RISM is based on a reduction to site-site, solute-solvent radially symmetrical distribution functions, there is a loss of infonnation about the tliree-dimensional spatial organization of the solvent density around a macromolecular solute of irregular shape. To circumvent this limitation, extensions of RISM-like theories for tliree-dimensional space (3d-RISM) have been proposed [81,82],... 

We recently proposed a new method referred to as RISM-SCF/MCSCF based on the ab initio electronic structure theory and the integral equation theory of molecular liquids (RISM). Ten-no et al. [12,13] proposed the original RISM-SCF method in 1993. The basic idea of the method is to replace the reaction field in the continuum models with a microscopic expression in terms of the site-site radial distribution functions between solute and solvent, which can be calculated from the RISM theory. Exploiting the microscopic reaction field, the Fock operator of a molecule in solution can be expressed by... 

Figure 4.1-11 The EXAFS data and pseudo-radial distribution functions of Co(ll) in (a) basic and (b) acidic chloroaluminate ionic liquid. Reproduced from reference 46 with permission.

Stochastic equation (A8.7) is linear over SP and contains the operators La and V.co of differentiation over time-independent variables Q and co. Therefore, if we assume that the time fluctuations of the liquid cage axis orientation Z(t) are Markovian, then the method used in Chapter 7 yields a kinetic equation for the partially averaged distribution function P(Q, co, t, E). The latter allows us to calculate the searched averaged distribution function... 

The anisotropy of the liquid crystal phases also means that the orientational distribution function for the intermolecular vector is of value in characterising the structure of the phase [22]. The distribution is clearly a function of both the angle, made by the intermolecular vector with the director and the separation, r, between the two molecules [23]. However, a simpler way in which to investigate the distribution of the intermolecular vector is via the distance dependent order parameters Pl+(J") defined as the averages of the even Legendre polynomials, PL(cosj r)- As with the molecular orientational order parameters those of low rank namely Pj(r) and P (r), prove to be the most useful for investigating the phase structure [22]. 

We turn now to the orientational correlations which are of particular relevance for liquid crystals that is involving the orientations of the molecules with each other, with the vector joining them and with the director [17, 28]. In principal they can be characterised by a pair distribution function but in view of the large number of orientational coordinates the representation of the multi-dimensional distribution can be rather difficult. An alternative is to use distance dependent orientational correlation coefficients which are related to the coefficients in an expansion of the distribution function in an appropriate basis set [17, 28]. 

We begin, however, with the singlet orientational distribution function which is shown for the three liquid crystal phases in Fig. 6. In each phase the distribution is peaked at cos of 1 showing that the preferred molecular orientation is parallel to the director. The form of the distribution function is well represented by the relatively simple function... 

A second simplihcation results from introducing the Born-Oppenheimer separation of electronic and nuclear motions for convenience, the latter is most often considered to be classical. Each excited electronic state of the molecule can then be considered as a distinct molecular species, and the laser-excited system can be viewed as a mixture of them. The local structure of such a system is generally described in terms of atom-atom distribution functions t) [22, 24, 25]. These functions are proportional to the probability of Ending the nuclei p and v at the distance r at time t. Building this information into Eq. (4) and considering the isotropy of a liquid system simplifies the theory considerably. 

Filming of atomic motions in liquids was thus accomplished. More specifically, the above experiment provides atom-atom distribution functions gpv(F, t) as they change during a chemical reaction. It also permits one to monitor temporal variations in the mean density of laser-heated solutions. Finally, it shows that motions of reactive and solvent molecules are strongly correlated the solvent is not an inert medium hosting the reaction [58]. 

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