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

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10.1063/1.2202316

### Abstract

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 and the internal conversion dynamics of 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-Tellerdynamics of the two excited states occurs on a time scale. The major part of the internal conversion to the ground state takes place within a short time scale of . This fast internal conversion is, however, incomplete and the remaining excited state population does not decay completely even within .

© 2006 American Institute of Physics

Received 09 March 2006
Accepted 12 April 2006
Published online 05 June 2006

Acknowledgments: Four of the authors (A.V., W.E., S.N., and W.D.) acknowledge financial support of the Bayerisch-Französisches Hochschulzentrum—Centre de Coopération Franco-Bavarois. One of the authors (U.M.) acknowledges support by the Sonderforschungsbereich 613 of the Deutsche Forschungsgemeinschaft. The authors are thankful to COST (Project No. D26/0006/02 “Dynamics of nonadiabatic processes”) and to the Chemistry Department of the CNRS (France) for additional financial support. The Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie are gratefully acknowledged for financial support. Large amounts of computing time have been generously provided by the Leibniz Rechenzentrum.

Article outline:

I. INTRODUCTION

II. THE SYSTEM

A. Symmetry considerations

B. Symmetry-adapted coordinates

C. Potential energy matrix and vibronic coupling pattern

D. *Ab initio* calculations

E. Fitting of the PES

III. DYNAMICAL INVESTIGATION

A. The method

B. Ionization to the ground state

C. Ionization to the excited state

1. Convergence considerations

2. Wave packet evolution

3. Photoelectron spectra

4. Population dynamics

IV. CONCLUSIONS

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2006-06-05

2014-04-23

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