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By means of STM measurements and fully self-consistent transport calculations we analyze how STM trajectories for the mapping of nanostructures on surfaces are affected by the atomic structure of the tip. For the particular case of carbon nanotubes we show that considerable distortions of the STM trajectory with respect to the actual structure, position and diameter of the nanotube can occur for certain tip geometries. Comparison between theory and experiment can allow to characterize and correct these distortions. [ABSTRACT FROM AUTHOR]

We study the alignment of the lattice structure of single walled carbon-nanotubes (SWNT) produced on a highly oriented pyrolytic graphite (HOPG) surface using controlled growth in ultrahigh vacuum (UHV). With scanning tunnelling microscopy (STM) at low temperature ( T=77 K) the HOPG and the SWNT were imaged in UHV simultaneously with atomic resolution. The lattice structure of the SWNT was compared to the HOPG. For this purpose we present a technique for evaluating the mutual orientation which uses the measured lattice vectors of the HOPG surface as a reference for distortion and drift effects in the STM image. The quantitative evaluation showed an alignment of the SWNT lattice structure to the structure of the substrate. [ABSTRACT FROM AUTHOR]

O-H bond stretching vibrations in hydrogen-bonded complexes embedded into cryogenic neon matrices are subtly downshifted from cold gas phase reference wavenumbers. To the extent that this shift is systematic, it enables neon matrices as more universally applicable spectroscopic benchmark environments for quantum chemical predictions. Outliers are indicative of either an assignment problem in one of the two cryogenic experiments or they reveal interesting dynamics or structural effects on the complexes as a function of the environment. We compile 6 literature-known pairs of experimental data in jet and neon matrix expansions and realize a 6-fold expansion of that number through targeted matrix isolation and/or slit jet expansion spectroscopy presented in this work. In many cases, the neon matrix shift is less than the uncertainty of the currently best-performing blind quantum chemical predictions for the gas phase, but in specific cases, it may exceed the currently achievable theoretical accuracy. Some evidence for a positive correlation of the matrix shift with the hydrogen bond shift is found, similar to observations for helium nanodroplets. Outliers in particular for water acting as a donor are discussed, and in a few cases they call for a future reinvestigation. Substantial improvement in the correlation of the matrix shift with the hydrogen bond shift is achieved for ketone monohydrates by removing a vibrational resonance. New insights into nitrile hydration isomerism are obtained, and the linear OH stretching spectrum of the jet-cooled ammonia-water complex is presented for the first time. Vibrational spectroscopy in weakly perturbing solid rare gas quantum matrices for the benchmarking of gas phase theory and future explicit theoretical treatments of the quantum matrix environment to better understand the outliers are both encouraged.

Vibrational spectroscopy in supersonic jet expansions is a powerful tool to assess molecular aggregates in close to ideal conditions for the benchmarking of quantum chemical approaches. The low temperatures achieved as well as the absence of environment effects allow for a direct comparison between computed and experimental spectra. This provides potential benchmarking data which can be revisited to hone different computational techniques, and it allows for the critical analysis of procedures under the setting of a blind challenge. In the latter case, the final result is unknown to modellers, providing an unbiased testing opportunity for quantum chemical models. In this work, we present the spectroscopic and computational results for the first HyDRA blind challenge. The latter deals with the prediction of water donor stretching vibrations in monohydrates of organic molecules. This edition features a test set of 10 systems. Experimental water donor OH vibrational wavenumbers for the vacuum-isolated monohydrates of formaldehyde, tetrahydrofuran, pyridine, tetrahydrothiophene, trifluoroethanol, methyl lactate, dimethylimidazolidinone, cyclooctanone, trifluoroacetophenone and 1-phenylcyclohexane- cis -1,2-diol are provided. The results of the challenge show promising predictive properties in both purely quantum mechanical approaches as well as regression and other machine learning strategies.

The procedure leading to the first HyDRA blind challenge for the prediction of water donor stretching vibrations in monohydrates of organic molecules is described. A training set of 10 monohydrates with experimentally known and published water donor vibrations is presented and a test set of 10 monohydrates with unknown or unpublished water donor vibrational wavenumbers is described together with relevant background literature. The rules for data submissions from computational chemistry groups are outlined and the planned publication procedure after the end of the blind challenge is discussed.