메뉴 건너뛰기




Volumn 108, Issue 31, 2004, Pages 6474-6486

From valence trapped to valence delocalized by bridge state modification in bis(triarylamine) radical cations: Evaluation of coupling matrix elements in a three-level system

Author keywords

[No Author keywords available]

Indexed keywords

APPROXIMATION THEORY; COUPLED CIRCUITS; ELECTRONS; MATRIX ALGEBRA; METHOD OF MOMENTS; POSITIVE IONS; POTENTIAL ENERGY; REDOX REACTIONS; SOLVENTS;

EID: 4143113317     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp048449s     Document Type: Article
Times cited : (118)

References (85)
  • 14
    • 84955415100 scopus 로고    scopus 로고
    • Balzani, V., Ed.; Wiley-VCH: Weinheim, Germany
    • Brunschwig, B. S.; Sutin, N. In Electron Transfer in Chemistry; Balzani, V., Ed.; Wiley-VCH: Weinheim, Germany, 2001; Vol. 2, pp 583-617.
    • (2001) Electron Transfer in Chemistry , vol.2 , pp. 583-617
    • Brunschwig, B.S.1    Sutin, N.2
  • 54
    • 33748485385 scopus 로고    scopus 로고
    • ab = -8.6 D. For more details about the application of the COSMO method to excited states, see: Klamt, A. J. Phys. Chem. 1996, 100, 3349-3353.
    • (1996) J. Phys. Chem. , vol.100 , pp. 3349-3353
    • Klamt, A.1
  • 55
    • 4143131972 scopus 로고    scopus 로고
    • note
    • The dipole moment of ions is not uniquely defined. We chose the center of gravity as the origin of the dipole moment vector which is equivalent to the center of the bridge.
  • 56
    • 4143126421 scopus 로고    scopus 로고
    • note
    • At the UHF level, all radical cations show strong charge localization at one triarylamine center and an asymmetrical structure. This broken symmetry effect is an inherent artifact of the UHF method.
  • 57
    • 4143153741 scopus 로고    scopus 로고
    • note
    • + in MeCN which should lead to a triarylamine localized asymmetric structure according to our experimental observations but remains in fact symmetrically delocalized.
  • 59
    • 4143094632 scopus 로고    scopus 로고
    • note
    • 11.
  • 60
    • 4143129710 scopus 로고    scopus 로고
    • note
    • + and the conclusions concerning the bridge mediated hopping remain valid because the electronic coupling has only a minor influence on the topology of the PES in these cases.
  • 61
    • 4143122039 scopus 로고    scopus 로고
    • note
    • + in Figure 5 is accurate to ∼ = 10%.
  • 63
    • 4143104490 scopus 로고    scopus 로고
    • Ph.D. Thesis, Universität Würzburg
    • Schelter, J. Ph.D. Thesis, Universität Würzburg, 2003.
    • (2003)
    • Schelter, J.1
  • 65
    • 4143115485 scopus 로고    scopus 로고
    • note
    • + in MeCN solvent by the COSMO method gave a symmetrical structure similar to the one in the gas phase. We assume this to be an artifact of the AMI parametrization, as explained in footnote 57.
  • 66
    • 4143081264 scopus 로고
    • Ph.D. Thesis, University of Regensburg
    • Knorr, A. Ph.D. Thesis, University of Regensburg, 1995.
    • (1995)
    • Knorr, A.1
  • 68
    • 4143092401 scopus 로고    scopus 로고
    • note
    • In our older publications, we assigned this transition to a π-π excitation of triarylamine radical cations in general. We now observed that this excitation is only observed for trianisylamine and dianisylarylamine radical cations at that particular position and intensity.
  • 69
    • 0041147803 scopus 로고
    • Brown, D. B., Ed.; D. Reidel Publishing Company: Dordrecht, The Netherlands
    • Hush, N. S. In Mixed-Valence Compounds; Brown, D. B., Ed.; D. Reidel Publishing Company: Dordrecht, The Netherlands, 1980; pp 151-188.
    • (1980) Mixed-valence Compounds , pp. 151-188
    • Hush, N.S.1
  • 78
    • 85056017459 scopus 로고    scopus 로고
    • note
    • -1/2; see ref 58.
  • 85
    • 0141917879 scopus 로고    scopus 로고
    • NIST Standard Reference Database Number 69; National Institute of Standards and Technology: Gaithersburg, MD, March
    • NIST Chemistry WebBook, NIST Standard Reference Database Number 69; Linstrom, P. J., Mallard, W. G., Eds.; National Institute of Standards and Technology: Gaithersburg, MD, March 2003 (http://webbook.nist.gov).
    • (2003) NIST Chemistry WebBook
    • Linstrom, P.J.1    Mallard, W.G.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.