Theoretical study of the predissociation of the A2Π State of ZnF including quasi-diabatisation of the spin-orbit coupling.

Abstract : The excited 2Π electronic states of ZnF have been diabatized in order to simulate the 2Π <- X2Sigma+ vibronic spectrum using a wavepacket propagation technique. The spin-orbit coupling functions within the 2Pi states and between the 2Π and B2Sigma+ states have also been diabatized, as well as the dipole and transition moment functions. As the adiabatic electronic 2Π states are strongly multi-configurational, the quasi-diabatisation scheme was based on the electronic wavefunction overlap along the reaction coordinate. The procedure leads to a repulsive 2Pi state reaching the first dissociation limit, Zn(1Sg) + F(2Pu), and a bound one associated with the second limit, Zn(3Pu) + F(2Pu)}. The adiabatic electronic potentials and coupling functions have been determined at the MRCI level of theory. The vibrational energies and the spin-orbit splittings are in agreement with early experimental data. The wavepacket propagation approach coupled with a Prony analysis allowed also to analyze the resonances and the bound vibronic states of the 2Π manifold. The 2Π <- X2Sigma+ vibronic spectra have been determined for Omega=1/2 and 3/2 originating to the v''=0 level of the X2 Sigma+ state.
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Submitted on : Saturday, October 20, 2012 - 6:52:18 AM
Last modification on : Thursday, July 18, 2019 - 4:36:05 PM

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Céline Léonard, Frédéric Le Quéré. Theoretical study of the predissociation of the A2Π State of ZnF including quasi-diabatisation of the spin-orbit coupling.. Journal of Chemical Physics, American Institute of Physics, 2012, 137 (16), pp.164318. ⟨10.1063/1.4762444⟩. ⟨hal-00743774⟩

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