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Article
An Excited Electron Avoiding a Positive Charge
Journal of Physical Chemistry Letters (2011)
  • Anthony D. Dutoi, University of the Pacific
  • Lorenz S. Cederbaum, Heidelberg University
Abstract
High-level ab initio calculations in the time domain reveal the effects of the chemistry in the vicinity of a chomophore unit on the dynamics of an initially localized electronic excitation. An all-electron wavepacket is propagated, and its one-body density matrix is used to divide the dynamic into particle and hole components that can be analyzed separately. The expectation that an excited electron will be attracted to a positively charged ammonium group is superseded by a dynamic in which the hole part of the excitation is driven away from this region, dragging the excited electron with it. These calculations illustrate the crucial role of the attraction between the particle and hole. Emerging time-domain electronic structure techniques hold much promise for unraveling the behavior of complex systems.
Keywords
  • charge separation,
  • density matrix,
  • electron correlation,
  • electronic dynamics,
  • fluorescent amino acid,
  • particle−hole attraction,
  • time domain
Publication Date
August 26, 2011
DOI
10.1021/jz200887k
Citation Information
Anthony D. Dutoi and Lorenz S. Cederbaum. "An Excited Electron Avoiding a Positive Charge" Journal of Physical Chemistry Letters Vol. 2 Iss. 18 (2011) p. 2300 - 2303 ISSN: 1948-7185
Available at: http://works.bepress.com/anthony-dutoi/3/