Abstract book - Prof. Per Jensen, Ph.D. - Bergische Universität ...

Invited Lectures, E2 95Theoretical Insights into the Spectroscopy of NO 3John F. Stanton 1 , Takatoshi Ichino 1 , Christopher S. Simmons 11 University of Texas at Austin, Austin, TX, USAKnowledge of the vibronic energy level structure associated with the electronic groundX 2 A 2 ’ state of the nitrate radical (NO 3 ) is assessed on the basis of existing experimentalobservations and a high-quality model Hamiltonian that has recently been constructed.It is conclusively demonstrated that the coupling between the X 2 A 2 ’ state and the B 2 E’electronic state (approximately 2 eV above it) has profound implications for the levelstructure and spectroscopy of the ground state; any sort of reasonable assignment of thelevels in terms of vibrational quantum numbers essentially becomes impossible only1500-2000 cm -1 above the zero-point level. Nevertheless, the energy levels predicted bythe vibronic Hamiltonian are in excellent agreement with positions that have beenobserved spectroscopically, although the interpretation of some of these states is inconflict with existing assignments. Three types of spectroscopy used to interrogate theground state of NO 3 – negative ion photodetachment, infrared absorption, and dispersedfluorescence – will be analyzed, the latter from approximately five upper B state levelsthat have recently been studied in the laboratory by Fukushima and collaborators.Stanton J.F.Ichino T.Simmons C.S.