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Article Dans Une Revue Journal of Chemical Physics Année : 2006

Photoionization-induced dynamics of ammonia: Ab initio potential energy surfaces and time-dependent wave packet calculations for the ammonia cation

Résumé

An analytical anharmonic six-dimensional three-sheeted potential energy surface for the ground and first excited states of the ammonia cation has been developed which is tailored to model the ultrafast photoinduced dynamics. Selected ab initio cuts, obtained by multireference configuration interaction calculations, have been used to determine the parameters of a diabatic representation for this Jahn-Teller and pseudo-Jahn-Teller system. The model includes higher-order coupling terms both for the Jahn-Teller and for the pseudo-Jahn-Teller matrix elements. The relaxation to the ground state is possible via dynamical pseudo-Jahn-Teller couplings involving the asymmetric bending and stretching coordinates. The photoelectron spectrum of NH3 and the internal conversion dynamics of NH+3 have been determined by wave packet propagation calculations employing the multiconfigurational time-dependent Hartree method. Three different time scales are found in the dynamics calculations for the second absorption band. The ultrafast Jahn-Teller dynamics of the two excited states occurs on a 5fs time scale. The major part of the internal conversion to the ground state takes place within a short time scale of 20fs. This fast internal conversion is, however, incomplete and the remaining excited state population does not decay completely even within 100fs.
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Dates et versions

hal-01118375 , version 1 (10-07-2017)

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Alexandra Viel, Wolfgang Eisfeld, Stefanie Neumann, Wolfgang Domcke, Uwe Manthe. Photoionization-induced dynamics of ammonia: Ab initio potential energy surfaces and time-dependent wave packet calculations for the ammonia cation. Journal of Chemical Physics, 2006, 124 (21), pp.214306. ⟨10.1063/1.2202316⟩. ⟨hal-01118375⟩
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