Dissociation rates for individual eigenstates ofS0formaldehyde: Fluctuations and barrier height

摘要

Spectra ofS0D2CO rovibronic states near the dissociation threshold have been taken with a new method by monitoringS1lifetime while Stark shifting anS1level through theS0manifold. An order of magnitude variation in the unimolecular dissociation rate and in theS1ndash;S0vibronic coupling matrix element is observed amongS0levels within a 0.2 cmminus;1energy range. These individual molecular eigenstates exhibit distinctive chemical properties. Dissociation rates averaged over an energy range of a few cmminus;1vary smoothly with energy and give a barrier height of 78.0ndash;81.1 kcal/mol for H2COrarr;H2+CO.