Connection between simple models and quantum chemical models for electron-transfer tunneling matrix element calculations: A Dyson's equations-based approach

Journal of Physical Chemistry

Volumn 100, Issue 28, 1996, Pages 11573-11580

  Balabin, Ilya A ^a   Onuchic, José Nelson ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CALCULATIONS; MATHEMATICAL MODELS; PHYSICAL CHEMISTRY;

DAYSON'S EQUATIONS; ELECTRON TRANSFER; QUANTUM CHEMICAL MODELS; TUNNELING ENERGY; TUNNELING MATRIX ELEMENT CALCULATIONS; WAVE FUNCTIONS;

CHARGE TRANSFER;

EID: 0030180687     PISSN: 00223654     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp953568g     Document Type: Article

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28. 2. Therefore, the ratio given by eq 5 makes ∈ = ∈̃.
29. |i-j|,1, where i, j > 0.
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31. t, given by eq 16, are, basically, dispersion relations (∈̃ can be considered to be a complex wave vector). Therefore, their branches are associated with modes.
32. 2/μ|, for zero overlap). Inclusion of overlap extends the range of validity of the expansion. In any case, the breakdown occurs at energies that are not physically relevant.
33. For physically relevant tunneling energies (close enough to the band), the solutions are real. Since we are primarily interested in ET at these energies, the analytical solutions are shown at Figures 3-8 and 10 only for the energies that they are real.
34. Connecting orbitals are the bridge orbitals directly coupled to D and A. They are represented by the indices i and j in eq 2. As expected, the intensity of these couplings will depend on the symmetry of D and A.
35. 12) may have to be included into the Hamiltonian.