ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The electronic interactions which promote singlet–singlet and triplet–triplet electronic excitation (energy) transfer (EET) are investigated in detail. Donor and acceptor locally excited configurations, ψ1(A*B) and ψ4(AB*), respectively, are each allowed to mix with bridging ionic configurations, ψ2(A+B−) and ψ3(A−B+) to form the new donor and acceptor wave functions ΨR=ψ1+λψ2+μψ3 and ΨP=ψ4+μψ2+λψ3. Use of the latter wave functions leads to the establishment of the matrix element TRP= 〈ΨR||H−E1||ΨP〉≈T14−(T12T24+T 13T34)/A, with Tij=〈ψi||H−E1||ψj〉 and A=E2−E1, as the exciton resonance interaction term for EET. Introduction of the Mulliken approximation shows that the "direct'' exciton resonance interaction term (T14) contributes primarily a Coulombic interaction, for singlet–singlet EET, while the "through–configuration'' exciton resonance interaction term [−(T12T24+T13T34)/A] replaces the Dexter exchange integral (which is a component of H14) as the primary source of short-range orbital overlap-dependent EET. The origins of "Dexter-type'' energy transfer are thus shown to be quite different from that originally outlined. © 1994 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.467869
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