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Volumn 106, Issue 21, 2002, Pages 5288-5296

Solvent mediated superexchange in a C-clamp shaped donor-bridge-acceptor molecule: The correlation between solvent electron affinity and electronic coupling

Author keywords

[No Author keywords available]

Indexed keywords

DONOR-BRIDGE-ACCEPTOR MOLECULE; ELECTRONIC COUPLING; MARCUS EQUATION; SOLVENT ELECTRON AFFINITY; SOLVENT MEDIATED SUPEREXCHANGE;

EID: 0037198823     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp014529+     Document Type: Article
Times cited : (28)

References (45)
  • 1
    • 0011526199 scopus 로고    scopus 로고
    • Electron transfer-from isolated molecules to biomolecules
    • Jortner, J., Bixon, M., Eds.; Wiley: New York
    • (a) Jortner, J., Bixon, M., Eds. Electron Transfer-From Isolated Molecules to Biomolecules. In Advances in Chemical Physics; Wiley: New York, 1999.
    • (1999) Advances in Chemical Physics
  • 9
    • 0011190498 scopus 로고    scopus 로고
    • The world "rigid" is used to indicate that the bridge has only one (not multiple) minimum energy conformation
    • The world "rigid" is used to indicate that the bridge has only one (not multiple) minimum energy conformation.
  • 17
    • 0011190499 scopus 로고    scopus 로고
    • note
    • 2 A qualitative analysis of this sort in a broad range of solvents is reported elsewhere. These comparisons provide good evidence that the electronic coupling is correlated to the solvent molecule's electron affinity, so that an electron mediated superexchange mechanism is operative for 1's photo-induced electron transfer.
  • 26
    • 0011180896 scopus 로고    scopus 로고
    • note
    • f, the donor only decay rate constant, is equated to the rate constant measured for the donor only analogue in the same solvent and temperature.
  • 27
    • 0000338046 scopus 로고
    • Details concerning the preparation of the DBA compound have been reported elsewhere
    • Details concerning the preparation of the DBA compound have been reported elsewhere. (a) Kumar, K.; Tepper, R. J.; Zeng, Y.; Zimmt, M. B. J. Org. Chem. 1995, 60, 4051.
    • (1995) J. Org. Chem. , vol.60 , pp. 4051
  • 28
    • 0011248710 scopus 로고    scopus 로고
    • Ph. D. Thesis, Brown University, Providence, RI
    • (b) Kaplan, R. Ph. D. Thesis, Brown University, Providence, RI, 2001.
    • (2001)
    • Kaplan, R.1
  • 32
    • 0011219160 scopus 로고    scopus 로고
    • note
    • The parameters in the continuum calculation (cavity radius, vacuum free energy difference and dipole moment change) were chosen to match the parameters in the molecular treatment. This choice allowed a direct comparison between the two models.
  • 33
    • 0001189810 scopus 로고    scopus 로고
    • note
    • The slopes found via the continuum model were 0.30 meV/K for 1,3-dichlorobenzene, 0.40 meV/K for chlorobenzene, 0.40 meV/K for chlorotoluene, and 0.12 meV/K for benzonitrile. Previous work (Vath, P.; Zimmt, M. B. J. Phys. Chem. A 2000, 104, 2626) showed that the continuum model underestimates the temperature dependence of the reaction free energy.
  • 34
    • 0011181174 scopus 로고    scopus 로고
    • note
    • -1 in benzonitrile.
  • 35
    • 0011255322 scopus 로고    scopus 로고
    • note
    • -1 in benzonitrile.
  • 37
    • 0011188457 scopus 로고    scopus 로고
    • note
    • -. The solvent dependence of the donor's ionization potential is assumed to be small. Hence, the electron affinity of the solvent gauges the change in energetics.
  • 39
    • 0011180897 scopus 로고    scopus 로고
    • note
    • The apparent, slight increase of the solvent reorganization energy with temperature (Figure 5) does not agree with the slight decrease observed in experiments or predicted by modern solvation theory. This slight difference is likely a result of the assumed temperature independence of the electronic coupling. See ref 22.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.