On the Zero-Point Energy of an Activated Complex and the Reaction 2NO+O2→2NO2

Abstract

Considerations, based on the uncertainty principle, have been brought forward which indicate that a reaction, whose rate is determined solely by a transitory activated complex in the formation of which classical degrees of freedom must be frozen out into vibrations, must have a positive activation energy at all temperatures, which increases with the temperature. A negative activation energy must mean the formation of a more or less stable intermediate compound, or ``molecular complex.'' The theory has been applied to the reaction 2NO+O2→2NO2.