Non-IPR C60 solids

J Chem Phys. 2009 Apr 28;130(16):164705. doi: 10.1063/1.3120287.

Abstract

Films comprising predominantly novel isomers of C(60) [=C(60)(nIPR)] have been generated by low energy ion beam deposition of vibronically excited C(60)(+) onto graphite followed by selective sublimation of C(60)(I(h)) from the deposited isomer mixture. The incident ions were generated by electron impact ionization/fragmentation of sublimed C(70). Images of the C(60)(nIPR) films obtained by applying atomic force microscopy show aggregates, which we attribute to covalently interlinked C(60)(nIPR) units. The covalent bonds are inferred from the significantly higher thermal stability of the C(60)(nIPR) films compared to the C(60)(I(h)) van der Waals solid-as measured by thermal desorption with mass spectrometric detection of the C(60) mass channel (the only desorbable species). In contrast to the characteristic doublet structure of the occupied valence band in the ultraviolet photoelectron spectrum of pure C(60)(I(h)), the valence band of C(60)(nIPR) films exhibits a triplet feature with the additional peak occurring at a binding energy of approximately 2.6 eV. This is an indicator of the electronic modifications induced by intermolecular bonding. C(60)(nIPR) films exhibit a narrower band gap than found for C(60)(I(h)). They also have significantly different chemical reactivity toward incorporation of thermal energy deuterium atoms. In order to model the experimental photoelectron spectra, various covalently linked oligomers of (#1809)C(60)(C(2v)), the second most stable conventional 60-atom fullerene cage, were calculated by means of the density functional theory. These spectral predictions together with analogous previous observations on related fullerene solids such as C(58) lead us to infer that C(60)(nIPR) films consist of fullerene cage isomers containing one or more adjacent pentagon pairs, which mediate covalent cage-cage interconnection.