Revisiting the von Neumann–Wigner noncrossing rule and validity of a dynamic correlation diagram method

Abstract

The noncrossing rule for potential energy surfaces can be applied only, as originally postulated by von Neumann and Wigner, to slowly occurring changes; it has, however, over many years, been widely used to rationalize fast chemical reactions. Taking the conversion of Dewar benzene to benzene as an example, we demonstrate a reaction that has a timescale for which crossings are allowed. Since it is now established that elementary chemical reactions proceed over ca. 10–100fs, as revealed experimentally by Zewail, the noncrossing rule cannot any longer be said to be valid for most chemical reactions. We further demonstrate that the mechanism of the chemiluminescent conversion of Dewar benzene to benzene is explained by an electronic state diagram derived using a dynamic correlation diagram method which allows crossings, whereas the reaction is not explained by a conventional approach, applying the noncrossing rule using a static correlation diagram method.