Valence State Atoms in Molecules. 5. Universal Scaling of the Inner Branch of Fifty RKR Potential Energy Curves. Comparison of the Valence State, Morse, and Rydberg Curves

Abstract

Achieving an unprecedented degree of universality, the valence state potential energy curve (VS−PEC) reproduces the inner branch of 50 “experimental” RKR−PECs to an accuracy of 1.14% average unsigned deviation. The scaled RKR curves of 50 molecules with calculated partial charges, 0 ≤ δ < 0.9, coalesce into virtually a single curve in the Coulson−Fischer range, 0.5 Re ≤ R ≤ 1.5Re, when plotted against qVS = z1/2(R − Re)/Re, with z = αeνe/2Be2. The ground-state dissociation energy De can be predicted from the equilibrium spectroscopic constants Be, νe, αe and the calculated VS promotion energy.