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Elucidating the Doping Effect on the Electronic Structure of Thiolate‐Protected Silver Superatoms by Photoelectron Spectroscopy
Author(s) -
Kim Kuenhee,
Hirata Keisuke,
Nakamura Katsunosuke,
Kitazawa Hirokazu,
Hayashi Shun,
Koyasu Kiichirou,
Tsukuda Tatsuya
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201901750
Subject(s) - superatom , x ray photoelectron spectroscopy , valence (chemistry) , icosahedral symmetry , binding energy , chemistry , crystallography , atomic orbital , electronic structure , doping , atom (system on chip) , spectroscopy , photoemission spectroscopy , atomic physics , electron , materials science , computational chemistry , nuclear magnetic resonance , physics , optoelectronics , organic chemistry , quantum mechanics , computer science , embedded system
Gas‐phase photoelectron spectroscopy (PES) was conducted on [XAg 24 (SPhMe 2 ) 18 ] − (X=Ag, Au) and [YAg 24 (SPhMe 2 ) 18 ] 2− (Y=Pd, Pt), which have a formal superatomic core (X@Ag 12 ) 5+ or (Y@Ag 12 ) 4+ with icosahedral symmetry. PES results show that superatomic orbitals in the (Au@Ag 12 ) 5+ core remain unshifted with respect to those in the (Ag@Ag 12 ) 5+ core, whereas the orbitals in the (Y@Ag 12 ) 4+ (Y = Pd, Pt) core shift up in energy by about 1.4 eV. The remarkable doping effect of a single Y atom (Y=Pd, Pt) on the electronic structure of the chemically modified (Ag@Ag 12 ) 5+ superatom was reproduced by theoretical calculations on simplified model systems and was ascribed to 1) the weaker binding of valence electrons in Y@(Ag + ) 12 compared to Ag + @(Ag + ) 12 due to the reduction in formal charge of the core potential, and 2) the upward shift of the apparent vacuum level due to the presence of a repulsive Coulomb barrier between [YAg 24 (SPhMe 2 ) 18 ] − and electron.