Structure and thermodynamics of self-assembled monolayers on gold nanocrystallites

Journal of Physical Chemistry B

Volumn 102, Issue 34, 1998, Pages 6566-6572

  Luedtke, W D ^a   Landman, Uzi ^a  

^a GEORGIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0008995616     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp981745i     Document Type: Article

References (39)

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32. The optimal structures of the gold cores were taken as those determined through simulations of bare gold clusters. Mass spectrometry, transmission electron miccroscopy, and X-ray measurements performed on isolated fractions of solution-phase prepared passivated gold crystallites confirmed that the structures of the gold cores of dodecanethiol passivated clusters are the same as those predicted in the simulations See: ref 7; Cleveland, C. L.; Landman, U.; Shafigullin, M.; Stephens, P. W.; Whetten, R. L. Z. Phys. D 1997, 40, 282.
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37. To distinguish between molecules in the core and boundary regions of the molecular bundles we calculated for each of the molecules the average (per chain) two-body nonbonded interactions between its segments and those of all the other molecules. For the bundled state the distribution of these intermolecular interaction energies is bimodal reflecting variations in the packing and coordination of the molecules; the boundary chains (BC), having roughly half the number of nearest neighbor chains compared to the fully coordinated chains at the core of the bundle, are characterized by higher (less negative) potential energy values. Therefore, molecules contributing to the higher energy component of the bimodal intermolecular interaction energy distribution were assigned as BC molecules and the other chains as belonging to the core (CC) of the bundle. Obviously, this distinction is valid only as long as the molecular bundle state maintains; for temperatures close to melting the high degree of disordering results in a broad energy distribution and the distinction between BC and CC molecules is not useful.
38. For an experimental confirmation of the predictions pertaining to bundling given in ref 17, see Wang, Z. L.; Harfenist, S. A.; Whetten, R. L.; Bentley, J.; Evans, N. D. J. Phys. Chem. B 1998, 102, 3068.
39. Luedtke W. D.; Landman, U., to be published. We note that in superlattices, bimodal bundles may form, as well as arrangements involving several oriented molecular bundles due to the more complex intercluster molecular packing constraints.