We tracked over time the conductance switching of single and bundled phenylene ethynylene oligomers isolated in matrices of alkanethiolate monolayers. The persistence times for isolated and bundled molecules in either the ON or OFF switch state range from seconds to tens of hours. When the surrounding matrix is well ordered, the rate at which the inserted molecules switch is low. Conversely, when the surrounding matrix is poorly ordered, the inserted molecules switch more often. We conclude that the switching is a result of conformational changes in the molecules or bundles, rather than electrostatic effects of charge transfer.

An earlier paper (Zatsarinny O and Froese Fischer C 2002 J. Phys. B: At. Mol. Opt. Phys. 35 4669) presented oscillator strengths for transitions from the 2p 2 3P term to high-lying excited states of carbon. The emphasis was on the accurate prediction of energy levels relative to the ionization limit and allowed transition data from the ground state. The present paper reports some refined transition probability calculations for transitions from 2p 2 3 P, 1 D, and 1 S to all odd levels up to 2p3d 3 P o . Particular attention is given to intercombination lines where relativistic effects are most important. 1 The customary unit cm −1 used here is related to the SI units of energy (joules) by 1 cm −1 = 1.986 445 61(34)× 10 −21 J [5].

Low-temperature scanning tunneling microscopy has been used to characterize the various structures of submonolayer and near-monolayer coverages of benzene (C6H6) on Au[111] at 4 K. At low coverage, benzene is found to adsorb preferentially at the top of the Au monatomic steps and is weakly adsorbed on the terraces. At near-monolayer coverage, benzene was found to form several long-range commensurate overlayer structures that depend on the regions of the reconstructed Au[111] surface, namely a (radical 52 x radical 52)R13.9 degrees structure over the hcp regions and a (radical 133 x radical 133)R17.5 degrees "pinwheel" structure over the fcc regions. Time-lapse imaging revealed concerted cascade motion of the benzene molecules in the (radical 133 x radical 133)R17.5 degrees pinwheel overlayer. We demonstrate that the observed cascade motion is a result of concerted molecular motion and not independent random motion.

We use self- and directed assembly to pattern organic monolayers on the nanometre scale. The ability of the scanning tunnelling microscope to obtain both nanometre-scale structural and electronic information is used to characterize patterning techniques, to elucidate the intermolecular interactions that drive them and to probe the structures formed. We illustrate three successful approaches: (1) phase separation of self-assembled monolayers by terminal and internal functionalization, (2) phase separation of self-assembled monolayers induced by post-adsorption processing and (3) control of molecular placement by insertion into a self-assembled monolayer. These methods demonstrate the possibilities of patterning films by exploiting the intrinsic properties of the molecules. We employ these methods to prepare matrix-isolated samples to probe molecular electronic properties of single and bundled molecules.

A digital image tracking algorithm based on Fourier-transform cross-correlation has been developed to correct for instrumental drift in scanning tunneling microscope images. A technique was developed to eliminate cumulative tracking errors associated with fractional pixel drift. This tracking algorithm was used to monitor conductance changes associated with different conformations in conjugated molecular switch molecules and to trace the diffusion of individual benzene molecules on Ag{110}. Molecular motions have been tracked for up to 25 h (400 images) of acquisition time.