Use of modern electron transfer theories to determine electronic coupling matrix elements in intramolecular systems

Journal of Physical Chemistry A

Volumn 102, Issue 28, 1998, Pages 5529-5541

  Kumar, Krishna ^a   Kurnikov, Igor V ^b   Beratan, David N ^b   Waldeck, David H ^b   Zimmt, Matthew B ^a  

^a BROWN UNIVERSITY   (United States)

^b UNIVERSITY OF PITTSBURGH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001027878     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp980113t     Document Type: Article

References (79)

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38. v and ω, a better choice for exploring the impact of individual parameters on |V| are S and ω. In this partitioning, the latter term only appears in the classical activation energy portion of eq 2, and the former appears in the nuclear tunneling factor.
39. -1.
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74. 43b were introduced to improve the virtual orbital description of excited donor states. The 3-21G and 6-311G basis sets were used in the Hartree-Fock calculations. CIS (configuration interaction singles) on the molecules were also employed to obtain the electronic coupling data. In this case, the coupling was calculated from the energy splitting of the two lowest CIS eigenstates that corresponded to donor and acceptor states. The donor and acceptor energies were shifted into resonance by attaching point charges to the donor and acceptor groups. The 3-21G basis set was used for CIS calculations. The CIS results agreed to within 30% with those derived using the Hartree-Fock/effective Hamiltonian method.
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