Molecular cluster model hydrogen bondings

The interaction model described above has been extensively tested and successfully used in many calculations on weak van der Waals as well as hydrogen bonded molecular clusters (see Hydrogen Bonding I and Hydrogen Bonding 2). It also forms the kernel of many solute/solvent potentials that are used in the various approaches to the modeling of solvation. 

Hydrogen-bonded clusters are an important class of molecular clusters, among which small water clusters have received a considerable amount of attention [148, 149]. Solvated cluster ions have also been produced and studied [150, 151]. These solvated clusters provide ideal model systems to obtain microscopic infonnation about solvation effect and its influence on chemical reactions. 

In many ways, the molecular models that we have used as the basis for our CAMD studies describe coal structure very well. However, none of the models investigated thus far contains explicit three-dimensional covalent cross-links. Actualfy, the models we have studied are primarily constructed of long chains of one-dimensionally-linked clusters with a number of short side-chains. However, it has been established on the basis of solvent swelling studies (11.15.16) that bituminous coal is primarily made up from a three-dimensional network of clusters held together by covalent bonds and by an even higher density of hydrogen bonds. These macromolecular models of coal, which are less concerned with the molecular structure than with the ways that clusters are bonded to one another, provide a complementary way of describing coal structure. 

The perturbation theories [2, 3] go a step beyond corresponding states the properties (e.g., Ac) of some substance with potential U are related to those for a simpler reference substance with potential Uq by a perturbation expansion (Ac = Aq + A + Aj + ). The properties of the simple reference fluid can be obtained from experimental data (or from simulation data for model fluids such as hard spheres) or corresponding states correlations, while the perturbation corrections are calculated from the statistical mechanical expressions, which involve only reference fluid properties and the perturbing potential. Cluster expansions involve a series in molecular clusters and are closely related to the perturbation theories they have proved particularly useful for moderately dense gases, dilute solutions, hydrogen-bonded liquids, and ionic solutions. 

It is known that first principles molecular dynamics may overcome the limitations related to the use of an intermolecular interaction model. However, it is not clear that the results for the structure of hydrogen bonding liquids predicted by first principles molecular dynamics simulations are necessarily in better agreement with experiment than those relying on classical simulations, and recent first principles molecular dynamics simulations of liquid water indicated that the results are dependent on the choice of different approximations for the exchange-correlation functional [50], Cluster calculations are an interesting alternative, although surface effects can be important and extrapolation to bulk phase remains a controversial issue. 

Some solid-state metal hydrides are commercially (and in some cases potentially) very important because they are a safe and efficient way to store highly flammable hydrogen gas (for example, in nickel-metal hydride (NiMH) batteries). However, from a structural and theoretical point of view many aspects of metal-hydrogen bonding are still not well understood, and it is hoped that the accurate analysis of H positions in the various interstitial sites of the previously described covalent, molecular metal hydride cluster complexes will serve as models for H atoms in binary or more complex solid state hydride systems. For example, we can speculate that the octahedral cavities are more spacious in which H atoms can rattle around , while tetrahedral sites have less space and may even have to experience some expansion to accommodate a H atom. 

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