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No Access Submitted: 09 June 2017 Accepted: 01 August 2017 Published Online: 15 August 2017

  • Tracking an electronic wave packet in the vicinity of a conical intersection

J. Chem. Phys. 147, 074101 (2017); https://doi.org/10.1063/1.4989462
Da-Long Qi1,2,a), Hong-Guang Duan2,3,4,a), Zhen-Rong Sun1, R. J. Dwayne Miller2,4,5, and Michael Thorwart3,4
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  • Da-Long Qi
  • Hong-Guang Duan
  • Zhen-Rong Sun
  • R. J. Dwayne Miller
  • Michael Thorwart
ABSTRACT
This work treats the impact of vibrational coherence on the quantum efficiency of a dissipative electronic wave packet in the vicinity of a conical intersection by monitoring the time-dependent wave packet projection onto the tuning and the coupling mode. The vibrational coherence of the wave packet is tuned by varying the strength of the dissipative vibrational coupling of the tuning and the coupling modes to their thermal baths. We observe that the most coherent wave packet yields a quantum efficiency of 93%, but with a large transfer time constant. The quantum yield is dramatically decreased to 50% for a strongly damped incoherent wave packet, but the associated transfer time of the strongly localized wave packet is short. In addition, we find for the strongly damped wave packet that the transfer occurs via tunneling of the wave packet between the potential energy surfaces before the seam of the conical intersection is reached and a direct passage takes over. Our results provide direct evidence that vibrational coherence of the electronic wave packet is a decisive factor which determines the dynamical behavior of a wave packet in the vicinity of the conical intersection.

ACKNOWLEDGMENTS

This work was supported by the Max Planck Society and the Excellence Cluster “The Hamburg Center for Ultrafast Imaging—Structure, Dynamics and Control of Matter at the Atomic Scale” of the Deutsche Forschungsgemeinschaft. D.-L. Qi thanks the Fund of ECNU for Overseas and Domestic Academic Visits for support. H.G.D. acknowledges financial support by the Joachim-Hertz-Stiftung Hamburg within a PIER fellowship. H.-G. Duan acknowledges help from Lipeng Chen for the wave packet projection calculations.

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  1. © 2017 Author(s). Published by AIP Publishing.

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