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We report on the synthesis, STM imaging and theoretical studies of thestructure, electronic structure and transport properties of linear chains ofstyrene and methyl-styrene molecules and their heterojunctions onhydrogen-terminated dimerized silicon (001) surfaces. The theory presented hereaccounts for the essential features of the experimental STM data including thenature of the corrugation observed along the molecular chains and thepronounced changes in the contrast between the styrene and methyl-styrene partsof the molecular chains that are observed as the applied bias is varied. Theobserved evolution with applied bias of the STM profiles near the ends of themolecular chains is also explained. Calculations are also presented of electrontransport along styrene linear chains adsorbed on the silicon surface atenergies in the vicinity of the molecular HOMO and LUMO levels. For shortstyrene chains this lateral transport is found to be due primarily to directelectron transmission from molecule to molecule rather than through the siliconsubstrate, especially in the molecular LUMO band. Differences between thecalculated position-dependences of the STM current around a junction of styreneand methyl-styrene molecular chains under positive and negative tip bias arerelated to the nature of lateral electron transmission along the molecularchains and to the formation in the LUMO band of an electronic state localizedaround the heterojunction.Comment: 17 pages plus 11 figures. To appear in Physical Review

Linear chains of styrene and methylstyrene molecules and their heterojunctions on silicon: Theory and experiment