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We investigate the ability of different density functional methods to describe the electronic properties of isolated gold clusters, self‐assembled monolayers (SAM) of oligophenylthiols (including the depolarization effect), and the biphenylthiol/gold interface. To elucidate the role of the exchange interaction, we consider a hierarchy of functionals including conventional (e.g., within the gradient corrected approximation), hybrid, and effective exact‐exchange functionals, namely the Localized Hartree–Fock (LHF) method, which is free from the self‐interaction‐error (SIE).We find that conventional exchange‐correlation functionals cannot well describe the energy‐level alignment at the metal/organic interface and predict a negligible metal‐molecule charge‐transfer. In addition, an overestimation of dipole moments and polarization effects are obtained in oligophenylthiols, leading to a wrong description of the SAM …
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Publication date: 
1 Oct 2010

Fabio Della Sala, Eduardo Fabiano, Savio Laricchia, Stefania D'Agostino, Manuel Piacenza

Biblio References: 
Volume: 110 Issue: 12 Pages: 2162-2171
International Journal of Quantum Chemistry