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Article Dans Une Revue Journal of Chemical Physics Année : 2016

Spin-orbit coupling in the dissociative excitation of alkali atoms at the surface of rare gas clusters: A theoretical study

Résumé

We analyze the role of the spin-orbit (SO) coupling in the dissociative dynamics of excited alkali atoms at the surface of small rare gas clusters. The electronic structure of the whole system is deduced from a one-electron model based on core polarization pseudo-potentials. It allows us to obtain in the same footing the energy, forces, and non-adiabatic couplings used to simulate the dynamics by means of a surface hopping method. The fine structure state population is analyzed by considering the relative magnitude of the SO coupling ξ, with respect to the spin-free potential energy. We identify three regimes of ξ-values leading to different evolution of adiabatic state population after excitation of the system in the uppermost state of the lowest np 2P shell. For sufficiently small ξ, the final population of the J=12 atomic states, P12, grows up linearly from P12=13 at ξ = 0 after a diabatic dynamics. For large values of ξ, we observe a rather adiabatic dynamics with P12 decreasing as ξ increases. For intermediate values of ξ, the coupling is extremely efficient and a complete transfer of population is observed for the set of parameters associated to NaAr3 and NaAr4 clusters.
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Dates et versions

hal-02396717 , version 1 (06-12-2019)

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D. Zanuttini, Julie Douady, Benoit Gervais. Spin-orbit coupling in the dissociative excitation of alkali atoms at the surface of rare gas clusters: A theoretical study. Journal of Chemical Physics, 2016, 144 (19), pp.194307. ⟨10.1063/1.4948814⟩. ⟨hal-02396717⟩
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