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

Poster session, D40 87The theoretical investigation of the shift of the degenerate vibrationsin the FSO 3 radicalUhlikova T.Urban S.Tereza Uhlíková, Štěpán UrbanInstitute of Chemical Technology, Department of Analytical Chemistry,Technická 5, 166 28, Prague 6, Czech Republic, tereza.uhlikova@vscht.czIt is experimentally proofed 1 that the ν 6(e) vibration of the ground state of the FSO 3 radicalis extremely stretched down from the expectation value according to the Born-Oppenheimer approximation. Calculations of the three lowest electronic states providedtheir symmetry X A 2, A E, and B E with T e ≈ 0, 1.0 and 2.4 eV, respectively. Consequently,the three double-degenerated e normal vibrations ν 6 (e), ν 5 (e), and ν 4 (e) can be inflluencedby vibronic interactions with excited states. The full problem of vibronic coupling ofnondegenerate state A 2 with an excited E state includes both pseudo-Jahn-Teller and Jahn-Teller effects which results in the (A+E) ⊗ (a 1 +e 1 +e 2 ) combination. The causes andstrenghs of the stretching down of the double-degenerated vibrations of the X A 2 due to thefirst excited state A E are studied in the frame of the linear vibronic coupling using KDC(Köppel, Domcke, and Cederbaum) model Hamiltonian.AcknowledgmentsThe work was supported through the Grant Agency of the Czech Academy of Sciences(Grants Nos.P206/10/2182, P206/10/P481, and 203/09/P306)References[1] H. Beckers, H. Willner, D. Grote, and W. Sander; J. Chem. Phys. 128, 084501, 2008