Molecular potential concept

In the second picture, an interfacial layer or region persists over several molecular diameters due to a more slowly decaying interaction potential with the solid (note Section X-7C). This situation would then be more like the physical adsorption of vapors (see Chapter XVII), which become multilayer near the saturation vapor pressure (e.g.. Fig. X-15). Adsorption from solution, from this point of view, corresponds to a partition between bulk and interfacial phases here the Polanyi potential concept may be used (see Sections X-7C, XI-1 A, and XVII-7). 

The single Slater determinant wavefunction (properly spin and symmetry adapted) is the starting point of the most common mean field potential. It is also the origin of the molecular orbital concept. 

The concept of corresponding states was based on kinetic molecular theory, which describes molecules as discrete, rapidly moving particles that together constitute a fluid or soHd. Therefore, the theory of corresponding states was a macroscopic concept based on empirical observations. In 1939, the theory of corresponding states was derived from an inverse sixth power molecular potential model (74). Four basic assumptions were made (/) classical statistical mechanics apply, (2) the molecules must be spherical either by actual shape or by virtue of rapid and free rotation, (3) the intramolecular vibrations are considered identical for molecules in either the gas or Hquid phases, and (4) the potential energy of a coUection of molecules is a function of only the various intermolecular distances. 

Breneman, C., and M. Martinov. 1996. The Use of the Electrostatic Potential Fields in QSAR and QSPR. In Molecular Electrostatic Potentials Concepts and Applications, edited by J. S. Murray and K. D. Sen. Elsevier, Amsterdam. 

The molecular potential energy surface is one of the most important concepts of physical chemistry. It is at the foundations of spectroscopy, of chemical kinetics and of the study of the bulk properties of matter. It is a concept on which both qualitative and quantitative interpretations of molecular properties can be based. So firmly is it placed in the theoretical interpretation of chemistry that there is a tendency to raise it above the level of a concept by ascribing it some physical reality. 

Molecular Electrostatic Potentials Concepts and Applications J.S. Murray and K. Sen (Editors)... 

The structure of this chapter is as follows. In Section II, after the concept of potential-energy surface and the coordinate systems in which the potential can be represented have been introduced, we describe the most important topographical characteristics of the molecular potential function. The general aspects, which refer to the calculation of the potential energy by ab initio methods, are analyzed in Section III. The need to develop efficient methods for the calculation of the potential function and the corresponding gradient in... 

Geerlings, R, Langenaeker, W., De Proft, F. and Baeten, A. (1996b). Molecular Electrostatic Potentials vs. DFT Descriptors of Reactivity. In Molecular Electrostatic Potentials Concepts and Applications (Murray, J.S. and Sen, K., eds.), Elsevier, Amsterdam (The Netherlands), pp. 587-617. [R]... 

---