Determination of interionic potentials in molecules

The rationale underlying materials by design is that properties are determined by structure so that if the relationships between structure and properties are understood, an appropriate material can be designed and fabricated to meet any set of criteria. Since ion-ion potentials determine state transformations and reactivity, they are essential to the entire concept of materials and molecules by design. Virtually all of the important state-to-state processes undergone by molecules (excitation, relaxation, ionization, dissociation, and combination) and the selection among these different pathways are determined by the ion-ion potentials and the resulting degree of overlap between molecular vibrational states for different electronic and atomic configurations. Although the depths of these potentials can be obtained from thermodynamic data and the separations between the vibronic states from spectroscopic measurements, the use of these potentials in the ab initio calculation of state-transformation outcomes is limited by the absence of any direct method for determining their extent and shape. The authors have recently developed a generalization of x-ray absorption fine structure (XAFS) and a related set of experimental and analysis procedures that, in principle, will allow them to obtain such potentials from XAFS data. They have undertaken the analysis of temperature-dependent XAFS data of Cu, Ag, and Au to test the accuracy of existing analytical forms (the Morse potential for metals) in predicting the details of pair distributions and to determine the range of validity of a temperature-independent effective pair-potential approximation. This is the final report of a three-year Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL)