Theoretical study of the predissociation of the A2Π State of ZnF including quasi-diabatisation of the spin-orbit coupling. - Archive ouverte HAL Access content directly
Journal Articles Journal of Chemical Physics Year : 2012

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

(1) , (1)
1

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.
Not file

Dates and versions

hal-00743774 , version 1 (20-10-2012)

Identifiers

Cite

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, 2012, 137 (16), pp.164318. ⟨10.1063/1.4762444⟩. ⟨hal-00743774⟩
51 View
0 Download

Altmetric

Share

Gmail Facebook Twitter LinkedIn More