Anharmonicity and the Jahn-Teller effect: The A2E" state of the nitrate radical NO₃

Abstract

Our recent expts. on the forbidden near IR transition A2E" X2A'2 of NO₃ have revealed that the dark A2E" state has a rich and well resolved rovibronic spectrum. This state, studied initially by Hirota and co-workers and Neumark and coworkers, is a Jahn-Teller state with two Jahn-Teller active modes, the degenerate bend v4 and stretch v3 modes. Furthermore, this state is coupled by the pseudo-Jahn-Teller effect with several nearby electronic states. The observation of a wide range of overtone and combination bands in this Herzberg-Teller allowed spectrum provides us with a means for exploring anharmonicity and higher order nonadiabatic couplings, both within the Jahn-Teller manifold and among the low lying electronic states.

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