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Volumn 112, Issue 34, 2008, Pages 13215-13225

Experimental and theoretical identification of valence energy levels and interface dipole trends for a family of (oligo)phenylene-ethynylenethiols adsorbed on gold

Author keywords

[No Author keywords available]

Indexed keywords

EMPIRICAL EVALUATIONS; INTERFACE DIPOLES; METAL-MOLECULE-METAL JUNCTIONS; MOLECULAR WIRES; SELF- ASSEMBLIES;

EID: 51749115509     PISSN: 19327447     EISSN: 19327455     Source Type: Journal    
DOI: 10.1021/jp8023183     Document Type: Article
Times cited : (20)

References (121)
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    • Kong, J.; White, C. A.; Krylov, A. I.; Sherrill, D.; Adamson, R. D.; Furlani, T. R.; Lee, M. S.; Lee, A. M.; Gwaltney, S. R.; Adams, T. R.; Ochsenfeld, C.; Gilbert, A. T. B.; Kedziora, G. S.; Rassolov, V. A.; Maurice, D. R.; Nair, N.; Shao, Y. H.; Besley, N. A.; Maslen, P. E.; Dombroski, J. P.; Daschel, H.; Zhang, W. M.; Korambath, P. P.; Baker, J.; Byrd, E. F. C.; Van Voorhis, T.; Oumi, M.; Hirata, S.; Hsu, C. P.; Ishikawa, N.; Florian, J.; Warshel, A.; Johnson, B. G.; Gill, P. M. W.; Head-Gordon, M.; Pople, J. A. J. Comput. Chem. 2000, 21, 1532.
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    • The ionization potential (IP) and electron affinity (EA) energies were determined with the following definitions: IP = E(cation)- E(neutral) and EA ≡ E(neutral)- E(anion).
    • The ionization potential (IP) and electron affinity (EA) energies were determined with the following definitions: IP = E(cation)- E(neutral) and EA ≡ E(neutral)- E(anion).
  • 109
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    • We note that a second possible reason for the required rigid shift of the DOS, as pointed out by one of the reviewers of this manuscript, could be due to the approximate nature of the exchange-correlation function used herein.
    • We note that a second possible reason for the required rigid shift of the DOS, as pointed out by one of the reviewers of this manuscript, could be due to the approximate nature of the exchange-correlation function used herein.
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    • Because of the hybrid nature of the B3LYP functional, neither compression nor expansion of the DOS was needed for these molecular systems, in contrast to other simulations of PES/IPES data (e.g., (a) Hill, I.G.; et al. Chem. Phys. Lett. 2000, 317, 444.
    • Because of the hybrid nature of the B3LYP functional, neither compression nor expansion of the DOS was needed for these molecular systems, in contrast to other simulations of PES/IPES data (e.g., (a) Hill, I.G.; et al. Chem. Phys. Lett. 2000, 317, 444.
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    • The rigid shifts for fitting of the PES spectra using the DFT DOS were as follows: OPE 3.34 eV; OPE-F 3.25 eV; OPE-NH2 3.59; OPENO2 3.23; and, 3.58 OPE-bisNO2
    • (c) Hwang; et al. J. Phys. Chem. C 2007, 111, 1378) The rigid shifts for fitting of the PES spectra using the DFT DOS were as follows: OPE 3.34 eV; OPE-F 3.25 eV; OPE-NH2 3.59; OPENO2 3.23; and, 3.58 OPE-bisNO2.
    • (2007) J. Phys. Chem. C , vol.111 , pp. 1378
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    • Recent studies of conjugated molecular SAMs, where the polar group is appended at the end of the molecule (e.g. refs 60, 81, 112, and 116), reveal rapid (exponential) decay of the electric field outside of the polar head group. For such systems, because of the distance between the head group and possible insulating effects of the remaining molecular backbone, it would be expected that image effects are small, if not negligible. The non-negligible image effects, observed in the present study, are proposed to arise from the placement of the dipolar groups along the side of the molecular backbone (thus negating any insulating effects of the backbone) and allowing differing orientations that permit the polar groups to become close to the substrate, therefore generating larger image effects.
    • Recent studies of conjugated molecular SAMs, where the polar group is appended at the end of the molecule (e.g. refs 60, 81, 112, and 116), reveal rapid (exponential) decay of the electric field outside of the polar head group. For such systems, because of the distance between the head group and possible "insulating" effects of the remaining molecular backbone, it would be expected that image effects are small, if not negligible. The non-negligible image effects, observed in the present study, are proposed to arise from the placement of the dipolar groups along the side of the molecular backbone (thus negating any insulating effects of the backbone) and allowing differing orientations that permit the polar groups to become close to the substrate, therefore generating larger image effects.
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    • For the purpose of comparison, a series of 4′-donor/acceptor- substituted 4-mercaptobiphenyls were evaluated at the B3LYP/6-3IG** level of theory (see Table 4 and Figure 11). The donor and acceptor substituents were chosen so as to repeat those reported in ref. 80 and to compare with those used in the present manuscript.
    • For the purpose of comparison, a series of 4′-donor/acceptor- substituted 4-mercaptobiphenyls were evaluated at the B3LYP/6-3IG** level of theory (see Table 4 and Figure 11). The donor and acceptor substituents were chosen so as to repeat those reported in ref. 80 and to compare with those used in the present manuscript.


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