title: Electronic structure tuning of diamondoids through functionalization.
abstract: We investigated the changes in electronic structures induced by chemical functionalization of the five smallest diamondoids using valence photoelectron spectroscopy. Through the variation of three parameters, namely functional group (thiol, hydroxy, and amino), host cluster size (adamantane, diamantane, triamantane, [121]tetramantane, and [1(2,3)4]pentamantane), and functionalization site (apical and medial) we are able to determine to what degree these affect the electronic structures of the overall systems. We show that unlike, for example, in the case of halobenzenes, the ionization potential does not show a linear dependence on the electronegativity of the functional group. Instead, a linear correlation exists between the HOMO-1 ionization potential and the functional group electronegativity. This is due to localization of the HOMO on the functional group and the HOMO-1 on the diamondoid cage. Density functional theory supports our interpretations.
authors: Institut für Optik und Atomare Physik, Technische Universität Berlin, EW 3-1, Hardenbergstr. 36, 10623 Berlin, Germany.
authors: Torbjörn
authors: T
authors: Rander
authors: Matthias
authors: M
authors: Staiger
authors: Robert
authors: R
authors: Richter
authors: Tobias
authors: T
authors: Zimmermann
authors: Lasse
authors: L
authors: Landt
authors: David
authors: D
authors: Wolter
authors: Jeremy E
authors: JE
authors: Dahl
authors: Robert M K
authors: RM
authors: Carlson
authors: Boryslav A
authors: BA
authors: Tkachenko
authors: Natalie A
authors: NA
authors: Fokina
authors: Peter R
authors: PR
authors: Schreiner
authors: Thomas
authors: T
authors: Möller
authors: Christoph
authors: C
authors: Bostedt