Conical and glancing Jahn-Teller intersections in the cyclic trinitrogen cation

PHYS 430

Vadim Mozhayskiy, mozhaysk@usc.edu and Anna I. Krylov, krylov@usc.edu. Department of Chemistry, University of Southern California, Los Angeles, CA 90089
The ground and electronically excited states of cyclic N3+ are characterized at the equilibrium D3h geometry and along the Jahn-Teller distortions. The lowest excited states are derived from single excitations from doubly degenerate HOMO to doubly degenerate LUMO, which gives rise to two exactly and two nearly degenerate states. The interaction of two degenerate states with two other states eliminates linear terms and results in a glancing rather than a conical Jahn-Teller intersection. Adiabatic PESs do not have singularities at the intersection point unless an accidental triple degeneracy occurs. Thus they have no geometric phase effect in the electronic wave functions. HOMO-2 to LUMO excitations give rise to two regular Jahn-Teller states. Stationary points of the excited states PESs are characterized. Cyclic N3 ionization potential is estimated to be 10.595 eV, in a good agreement with recent experiments. Photoelectron spectrum of cyclic N3 in the energy range Eex < 14 eV is predicted to be dominated by the transitions between the lowest electronic states of neutral N3 and the ground state of the cation.
 

Poster Session
7:30 PM-10:00 PM, Wednesday, 13 September 2006 Moscone Center -- Hall D, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, 11 September 2006 Moscone Center -- Hall D, Sci-Mix

Division of Physical Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006