THE BEHAVIOR OF THE RYDBERG-KLEIN-REES (RKR) METHOD NEAR THE DISSOCIATION LIMIT
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Date
1973
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Publisher
Ohio State University
Abstract
It is well known that Rydberg-Klein-Rees (RKR) potential curves often display irregular behavior as the dissociation limit is approached, particularly on the inner wall. This irregular behavior is not found in, e.g., ab initio potentials and is an artifact of the RKR method. In particular, the $G_{v}$ and $B_{v}$ input for v $\rightarrow$ dissociation are (a) experimentally relatively uncertain, (b) often dependent primarily on the long-range region near $R_{v+}$ and not on the inner wall near $R_{v-}$, and (c) often seriously perturbed in a diffuse (i.e., multistate and/or continuum) sense. Because of the frequent lack of sensitivity to the inner wall in the RKR input, other (new) methods such as discrete analogs of the behavior of the Condon Reflection method or the direct construction of the function $\partial V/\partial R$ may be more useful in obtaining a reliable inner wall.
Description
Acknowledgment is made to the Donors of the Petroleum Research Fund, administered by the American Chemical Society, for support of this research. William C. Stwalley has been an Alfred P. Sloan Foundation Fellow.
Author Institution: Department of Chemistry, University of Iowa; Department of Chemistry, Wartburg College
Author Institution: Department of Chemistry, University of Iowa; Department of Chemistry, Wartburg College