We report two-dimensional electron energy-loss spectra of CO_{2}. The high-resolution experiment reveals a counterintuitive fine structure at energy losses where CO_{2} states form a vibrational pseudocontinuum. Guided by the symmetry of the system, we constructed a four-dimensional nonlocal model for the vibronic dynamics involving two shape resonances (forming a Renner-Teller Π_{u} doublet at the equilibrium geometry) coupled to a virtual Σ_{g}^{+} state. The model elucidates the extremely non-Born-Oppenheimer dynamics of the coupled nuclear motion and explains the origin of the observed structures. It is a prototype of the vibronic coupling of metastable states in continuum.

Charles University Faculty of Mathematics and Physics Institute of Theoretical Physics 5 Holešovičkách 2 180 00 Prague 8 Czech Republic

J Heyrovský Institute of Physical Chemistry Czech Academy of Sciences Dolejškova 2155 3 182 23 Prague 8 Czech Republic

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