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Organic Molecular Crystals: Charge-Transfer Complexes

  • Zoltän G. Soos
  • Douglas J. Klein

Abstract

Solutions of electron donors (D) and acceptors (A) exhibit absorptions not associated with either individual molecule.(1) Mulliken(2) proposed that the new absorptions involve an electron transfer from D to A, as indicated by
$${{\psi }_{complex}}\left( DA \right)\underrightarrow{h{{v}_{CT}}}{{\psi }_{complex}}\left( {{D}^{+}}{{A}^{-}} \right)$$
(1)
Here hv CT is the charge-transfer (CT) excitation energy, and the CT band is explicitly associated with the molecular complex formed between a D and an A molecule. The nature of such DA complexes has been the subject of extensive experimental and theoretical studies.(3–5) The energetics of dimer formation; the geometry of the complex; the systematics of varying D, A, and solvents; and the nature of CT absorption have been explored. The CT excitation is greatly enhanced,(3,4,6) as suggested by Mulliken,(2) via small ad-mixtures of the excited singlet configuration 1|D+A> into the ground state, |DA> However, the additional configuration-interaction stabilization due to this small admixture does not(6,7) usually dominate the binding energy or the geometry of the complex. As we will discuss in Section 2, the full quantum-mechanical treatment of a DA dimer thus requires explicit consideration of a variety of intermolecular forces.

Keywords

Hubbard Model Molecular Crystal Complex Salt Site Energy Minimum Basis 
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.

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Copyright information

© Bell Telephone Laboratories, Incorporated 1976

Authors and Affiliations

  • Zoltän G. Soos
    • 1
  • Douglas J. Klein
    • 2
  1. 1.Department of ChemistryPrinceton UniversityPrincetonUSA
  2. 2.Department of PhysicsUniversity of TexasAustinUSA

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