IMPOSING A MECHANICAL MODEL ON AN IRREGULAR ELECTRONIC STATE: THE $A\,^1\Sigma^+$ STATE OF AgH
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Date
2005
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Publisher
Ohio State University
Abstract
Almost since its first observation in 1925, it has been clear that the $A\,^1\Sigma^+$ state of AgH is irregular, in that its level energy patterns and isotope effects resisted conventional systematic description.} {\bf 72}, 163 (1931).} A proposal by Ger{o} and Schmid} and R.\ Schmidt, {\em Z.\ Physik} {\bf 121}, 459 (1943).} that this irregular behaviour was due to perturbation by the nearby $B\,^1\Sigma^+$ state was disputed by Learner,} {\bf A\,269}, 327 (1962).} who argued that the problem was due to an avoided crossing which gives rise to a ``shelf'' on the outer part of the potential well. Recent {\em ab initio} studies by Witek {\em et al.}} {\bf 113}, 8015 (2000).}$^,$} {\bf 116}, 8386 (2002).} suggest that the irregular behaviour is actually due to two avoided crossings, and that the resulting effective potential has what we call ``anti-shelf'' behaviour which is qualitatively different than that described by Learner.$^c$ The present paper describes our efforts to determine an accurate effective potential function and delineate the degree and nature of residual non-mechanical behaviour for this state from a combined-isotopologue analysis of all available experimental data.
Description
{\,E.\ Bengtsson and E.\ Olsen, {\em Z.\ Physik{\,L.\ Ger{o{\,R.C.M.\ Learner, {\em Proc.\ Roy.\ Soc.\ (London){\,H.A.\ Witek, T.\ Nakijima and K.\ Hirao, {\em J.\ Chem.\ Phys.{\,H.A.\ Witek, D.G.\ Fedorov, K.\ Hirao, A.\ Viel and P.-O.\ Widmark, {\em J.\ Chem.\ Phys.
Author Institution: Guelph-Waterloo Centre for Graduate Work in Chemistry and; Biochemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
Author Institution: Guelph-Waterloo Centre for Graduate Work in Chemistry and; Biochemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada