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Volumn 106, Issue 10, 2002, Pages 1917-1925

The role played by orbital energetics in solvent mediated electronic coupling

Author keywords

[No Author keywords available]

Indexed keywords

ORBITAL ENERGETICS;

EID: 0037076066     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp011603f     Document Type: Article
Times cited : (16)

References (66)
  • 17
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    • manuscript in preparation
    • Evidence for a temperature dependence of solvent mediated coupling in C-shaped DBA molecules has been found. Napper, A.; Read, I.; Zimmt, M.B.; Waldeck, D.H., manuscript in preparation.
    • Napper, A.1    Read, I.2    Zimmt, M.B.3    Waldeck, D.H.4
  • 18
    • 0011111006 scopus 로고    scopus 로고
    • note
    • A similar analysis of solvent effects on electron transfer rates in highly curved molecules was previously reported. See ref 6a.
  • 20
    • 0011076924 scopus 로고    scopus 로고
    • Ph.D. Thesis, Brown University
    • (b) Han, H. Ph.D. Thesis, Brown University, 1998.
    • (1998)
    • Han, H.1
  • 21
    • 0011111252 scopus 로고    scopus 로고
    • Ph.D. Thesis, Brown University
    • (c) Kaplan, R. Ph.D. Thesis, Brown University, 2001.
    • (2001)
    • Kaplan, R.1
  • 22
    • 0011106011 scopus 로고    scopus 로고
    • note
    • Charge-transfer distances determined using the Generalized Mulliken Hush Methodol. See ref 12.
  • 25
    • 0011077408 scopus 로고    scopus 로고
    • note
    • This conclusion is supported by prior determinations of |V| for 1 in three of these solvents; ether, acetonitrile and benzonitrile. See ref 3c.
  • 29
    • 0011105529 scopus 로고    scopus 로고
    • note
    • Molecular solvation models developed by Matyushov incorporate solvent density contributions and reproduce FCWDS variations with temperature accurately. See ref 7, 15.
  • 30
    • 0011142317 scopus 로고    scopus 로고
    • note
    • OX = 0.87 V. All potentials were measured relative to the Ag/AgCl electrode.
  • 31
    • 0011135764 scopus 로고
    • Ph.D. Thesis, Brown University
    • 1 state of the donor varies between 2.98 and 3.04 eV in these solvents. See Kumar, K. Ph.D. Thesis, Brown University, 1995.
    • (1995)
    • Kumar, K.1
  • 40
    • 0011141631 scopus 로고    scopus 로고
    • note
    • As noted above, the coupling across the bridge of 1 is presumed to be solvent independent. Thus, only the FCWDS vary with solvent.
  • 41
    • 0011142126 scopus 로고    scopus 로고
    • note
    • Including all solvents, the calculated FCWDS ratio is 0.085 ± 0.034.
  • 42
    • 0011082116 scopus 로고    scopus 로고
    • note
    • -1 1 from a prior evaluation was used. See ref 3c.
  • 43
    • 0011082791 scopus 로고    scopus 로고
    • note
    • 2CN 6.9, PhCN 5.5, o-dichlorobenzene 8.4.
  • 44
    • 0011082792 scopus 로고    scopus 로고
    • note
    • ref of this magnitude are certainly possible given the presence of electrolyte in the redox measurements.
  • 45
    • 0011141632 scopus 로고    scopus 로고
    • note
    • 2 was 4.2-fold larger than that obtained in the present analysis. At this point, it is not possible to determine if the larger disparity arises from errors in the parameters used to determine FCWDS(T) or from a stronger temperature dependence of |V| in this solvent.
  • 47
    • 0011135765 scopus 로고    scopus 로고
    • note
    • Solvent refractive index may also contribute to Δ as the solvent electronic polarizability also solvates the superexchange state.
  • 49
    • 0000638021 scopus 로고
    • Discussions of the origin of this offset may be found in the following citations. (a) Chen, D.; Gallup, G.A. J. Chem. Phys. 1990, 93, 8893.
    • (1990) J. Chem. Phys. , vol.93 , pp. 8893
    • Chen, D.1    Gallup, G.A.2
  • 54
    • 0011115171 scopus 로고    scopus 로고
    • note
    • The absence of literature dielectric constant data for 1,3-dithiolane prevents calculation of the FCWDS in this solvent.
  • 58
    • 0011115172 scopus 로고    scopus 로고
    • note
    • -1.
  • 61
    • 0003930168 scopus 로고
    • John-Wiley and Sons: Chichester, Table 6.4
    • (a) Marcus, Y. Ion Solvation, John-Wiley and Sons: Chichester, 1985. Table 6.4.
    • (1985) Ion Solvation
    • Marcus, Y.1
  • 63
    • 0011077410 scopus 로고    scopus 로고
    • note
    • CC in 2 could vary with solvent polarity and influence its electron-transfer kinetics. The extent of this Coulomb driven reduction of the D/A separation, if it occurs in solution, should be largest in solvents with the smallest dielectric constants. The observed variation of |V(2)| is not correlated with dielectric constant.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.