title: On the opto-electronic properties of phosphine and thiolate-protected undecagold nanoclusters.
abstract: We present here a detailed time-dependent density-functional theory investigation aimed at systematically dissecting the electronic spectra of two thiolate and phosphine protected undecagold nanoclusters. Calculations performed on the experimental structures of Au11(PPh3)7Cl3 and Au11(PPh3)7(SPyr)3 show that ligands have negligible contributions in the visible region. Metal → ligand charge transfer transitions appear at energies well above the visible threshold, while transitions with some small ligand → metal and ligand → ligand character occur sporadically at even higher energies. Thus, the conjugation effect between the π-electrons of the ligand and electrons of gold, recently hypothesized to interpret the spectra of phosphine and thiolate-protected nanoclusters, is not confirmed by the results of this study.
authors: University of Modena an Reggio Emilia (UniMoRE), Dept. of Chemical and Geological Sciences (DSCG), Via Campi 183, Modena, 41125, Italy. francesco.munizmiranda@unimore.it alfonso.pedone@unimore.it.
authors: Francesco
authors: F
authors: Muniz-Miranda
authors: Maria Cristina
authors: MC
authors: Menziani
authors: Alfonso
authors: A
authors: Pedone
mesh_terms: D004583:Electrons; D008024:Ligands; D053768:Metal Nanoparticles / Q000737:chemistry*; D050607:Organogold Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D011789:Quantum Theory; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D008024:Ligands; D050607:Organogold Compounds; D010720:Phosphines; D013438:Sulfhydryl Compounds; C035797:undecagold; C044646:phosphine