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Hierarchical Effective-Mode Approach for Extended Molecular Systems

  • Rocco Martinazzo
  • Keith H. Hughes
  • Irene Burghardt
Chapter
Part of the Progress in Theoretical Chemistry and Physics book series (PTCP, volume 22)

Abstract

Photoinduced processes in extended molecular systems are often ultrafast and involve strong electron-vibration (vibronic) coupling effects which necessitate a non-perturbative treatment. In the approach presented here, high-dimensional vibrational subspaces are expressed in terms of effective modes, and hierarchical chains of such modes which sequentially resolve the dynamics as a function of time. This permits introducing systematic reduction procedures, both for discretized vibrational distributions and for continuous distributions characterized by spectral densities. In the latter case, a sequence of spectral densities is obtained from a Mori/Rubin-type continued fraction representation. The approach is suitable to describe nonadiabatic processes at conical intersections, excitation energy transfer in molecular aggregates, and related transport phenomena that can be described by generalized spin-boson models.

Keywords

Spectral Density Effective Mode Conical Intersection Photoinduced Process Subsystem Operator 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgments

Various contributions to the effective-mode developments described here, notably by Lorenz Cederbaum, Etienne Gindensperger, Eric Bittner, and Hiroyuki Tamura, are gratefully acknowledged.

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Copyright information

© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  • Rocco Martinazzo
    • 1
  • Keith H. Hughes
    • 2
  • Irene Burghardt
    • 3
    • 4
  1. 1.Department of Physical Chemistry and ElectrochemistryUniversity of MilanMilanItaly
  2. 2.School of ChemistryBangor UniversityBangorUK
  3. 3.Département de ChimieEcole Normale SupérieureParisFrance
  4. 4.Institute of Physical and Theoretical ChemistryGoethe University FrankfurtFrankfurtGermany

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