Effects of multimode Jahn-Teller coupling on the photodetachment spectrum of nitrate anion (NO^-₃)

Abstract

The multimode static and dynamic Jahn-Teller effects in the ²E″ and ²E′ excited states of the nitrate radical (NO₃) and their impact on the vibronic structure of the photodetachment spectrum of the nitrate anion are investigated theoretically. The analysis rests on the quadratic vibronic coupling approach and large-scale multi-reference configuration interaction calculations for the determination of the respective coupling parameters. The possible pseudo-Jahn-Teller interactions between the ground ²A₂′ and excited ²E′ electronic states of NO₃ are also included in the vibronic coupling model. The results of the ²E″ state are compared with the experimental recording of Neumark and co-workers, while those for the ²E′ state come as a prediction. The deviations between theoretical and experimental vibronic structures of the ²E″ photoelectron band are discussed.