title: Experimental and theoretical study of the absorption properties of thiolated diamondoids.
abstract: Nanoscale hybrid systems are a new class of molecular aggregates that offer numerous new possibilities in materials design. Diamondoid thiols are promising nanoscale building blocks for such hybrid systems. They allow the incorporation of functional groups and the investigation of their effects on the unique materials' properties of diamondoids. Here we combine experimental data with ab initio theory to explore the optical properties of diamondoid thiols and their dependence on size and shape. Agreement between theoretically and experimentally obtained absorption spectra allows the identification of the nature of the optical transitions that are responsible for some photophysical and photochemical processes. We show that the optical properties of diamondoid thiols in the deep UV regime depend on the functionalization site but are largely size independent. Our findings provide an explanation for the disappearance of diamondoid UV photoluminescence upon thiolation for smaller diamondoids. However, our theoretical results indicate that for larger diamondoid thiols beyond the critical size of six diamondoid cages the lowest energy transitions are characterized by diamondoidlike states suggesting that UV luminescence may be regained.
authors.affiliation: Institut fur Optik und Atomare Physik, Technische Universität Berlin, Eugene-Wigner-Bldg., EW 3-1, Hardenbergstr. 36, Berlin 10623, Germany.
authors.forename: Lasse
authors.initials: L
authors.lastname: Landt
authors.forename: Christoph
authors.initials: C
authors.lastname: Bostedt
authors.forename: David
authors.initials: D
authors.lastname: Wolter
authors.forename: Thomas
authors.initials: T
authors.lastname: Möller
authors.forename: Jeremy E P
authors.initials: JE
authors.lastname: Dahl
authors.forename: Robert M K
authors.initials: RM
authors.lastname: Carlson
authors.forename: Boryslav A
authors.initials: BA
authors.lastname: Tkachenko
authors.forename: Andrey A
authors.initials: AA
authors.lastname: Fokin
authors.forename: Peter R
authors.initials: PR
authors.lastname: Schreiner
authors.forename: Alexander
authors.initials: A
authors.lastname: Kulesza
authors.forename: Roland
authors.initials: R
authors.lastname: Mitrić
authors.forename: Vlasta
authors.initials: V
authors.lastname: Bonacić-Koutecký
mesh_terms: D003198:Computer Simulation; D018130:Diamond / Q000737:chemistry*; D008956:Models, Chemical; D049329:Nanostructures / Q000737:chemistry; D010316:Particle Size; D011789:Quantum Theory; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D013438:Sulfhydryl Compounds; D018130:Diamond