Oxygen-Induced 1D to 2D Transformation of On-Surface Organometallic Structures.

While surface-confined Ullmann-type coupling has been widely investigated for its potential to produce π-conjugated polymers with unique properties, the pathway of this reaction in the presence of adsorbed oxygen has yet to be explored. Here, the effect of oxygen adsorption between different steps of the polymerization reaction is studied, revealing an unexpected transformation of the 1D organometallic (OM) chains to 2D OM networks by annealing, rather than the 1D polymer obtained on pristine surfaces. Characterization by scanning tunneling microscopy and X-ray photoelectron spectroscopy indicates that the networks consist of OM segments stabilized by chemisorbed oxygen at the vertices of the segments, as supported by density functional theory calculations. Hexagonal 2D OM networks with different sizes on Cu(111) can be created using precursors with different length, either 4,4″-dibromo-p-terphenyl or 1,4-dibromobenzene (dBB), and square networks are obtained from dBB on Cu(100). The control over size and symmetry illustrates a versatile surface patterning technique, with potential applications in confined reactions and host-guest chemistry.

Self-assembly of indole-2-carboxylic acid at graphite and gold surfaces.

Model systems are critical to our understanding of self-assembly processes. As such, we have studied the surface self-assembly of a small and simple molecule, indole-2-carboxylic acid (I2CA). We combine density functional theory gas-phase (DFT) calculations with scanning tunneling microscopy to reveal details of I2CA assembly in two different solvents at the solution/solid interface, and on Au(111) in ultrahigh vacuum (UHV). In UHV and at the trichlorobenzene/highly oriented pyrolytic graphite (HOPG) interface, I2CA forms epitaxial lamellar structures based on cyclic OH⋯O carboxylic dimers. The structure formed at the heptanoic acid/HOPG interface is different and can be interpreted in a model where heptanoic acid molecules co-adsorb on the substrate with the I2CA, forming a bicomponent commensurate unit cell. DFT calculations of dimer energetics elucidate the basic building blocks of these structures, whereas calculations of periodic two-dimensional assemblies reveal the epitaxial effects introduced by the different substrates.

An Algorithm to Estimate the Power Spectral Density From Allan Deviation.

Complex architectures for wireless communications, digital electronics, and space-based navigation interlink several oscillator-based devices such as clocks, transponders, and synthesizers. Estimators characterizing their stability are critical for addressing the impact of random fluctuations (noise) on the overall system performance. Manufacturers typically specify this as an Allan/Hadamard Variance (AVAR/HVAR) profile in the time domain. However, stochastic processes constituting the noise are more thoroughly described in the frequency domain by the power spectral density function (PSD). Both are second-moment measures of the time series, but it is only possible to translate unambiguously from the PSD to the AVAR/HVAR, not vice versa, except in the case of a single noise type, a rather unrealistic case. This note presents an analytical method to generate an approximated PSD expressed as a set of power-laws defined in specific intervals in the frequency domain, starting from an AVAR/HVAR expressed as a set of power-laws in the time domain. The proposed algorithm is straightforward to implement, applicable to all noise types (and combinations thereof), and can be self-validated by reconstructing the corresponding AVAR/HVAR by direct computation. Coupling with well-established algorithms relying on the PSD for power-law noise generation, the ensuing method encompasses the capability for generating multicolored noise in end-to-end simulations, as demonstrated hereby for NASA's deep space atomic clock. We also report on the limitations of the algorithm and analytical expressions of the continuous version of the algorithm.

Calcaneal osteotomies.

The current trend is to preserve the hindfoot joints to allow for more normal biomechanics and avoid arthritic changes in adjacent joints. Calcaneal osteotomies are effective in the treatment of hindfoot and foot malalignment with an acceptable rate of complications at medium-term follow-up. An important prerequisite should be flexibility and the absence of joint arthritis.