Collect. Czech. Chem. Commun. 1998, 63, 1143-1151

Two Classes of ZEKE Spectroscopy

Heinrich L. Selzlea, Edward W. Schlaga, Françoise Remacleb and Raphael D. Levinec

a Institut für physikalische und theoretische Chemie, Technische Universität Munchen, D-85747 Garching, Germany
b Departement de Chimie, B6, Université de Liege, B 4000 Liege, Belgium
c The Fritz Haber Research Center for Molecular Dynamics, The Hebrew University, Jerusalem 91904, Israel and Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles, CA 9002-1569, U.S.A.


A classification of ZEKE spectra into two classes based on operational criteria is useful for discussion. The proposal is that some of the different and seemingly conflicting effects reported for different molecular (or the same molecule for different excitations), such as the role of an external field, are due to these two distinct classes of states which can be optically accessed. Class A is the direct, "front door" entry where the states excited are those which are detected by the delayed ionization. Class B is a very prevalent but indirect "backdoor" route where it is only the interaction of the Rydberg electron with the core, possibly aided by external perturbations, that allows a signal to be detected upon ionization. The operational criteria for distinguishing between or even exploiting the features of the two classes are discussed. Such attention might be useful as new techniques for class B spectra are developed.

Keywords: Zero electron kinetic energy; ZEKE spectroscopy; Electric field; Rydberg; Core interaction; Frank-Condon; Nitric oxide cation.