scholarly journals Direct observation of knock-on reaction with umbrella inversion arising from zero-impact-parameter collision at a surface

2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Matthew J. Timm ◽  
Lydie Leung ◽  
Kelvin Anggara ◽  
John C. Polanyi
Keyword(s):  
Impact Parameter ◽  
Chemical Reactions ◽  
Degrees Of Freedom ◽  
Copper Surface ◽  
Collision Partner ◽  
Scanning Tunnelling ◽  
Tunnelling Microscopy ◽  
Newton’S Cradle ◽  
Miss Distance ◽  
The Impact

AbstractIn Surface-Aligned-Reactions (SAR), the degrees of freedom of chemical reactions are restricted and therefore the reaction outcome is selected. Using the inherent corrugation of a Cu(110) substrate the adsorbate molecules can be positioned and aligned and the impact parameter, the collision miss-distance, can be chosen. Here, substitution reaction for a zero impact parameter collision gives an outcome which resembles the classic Newton’s cradle in which an incident mass ‘knocks-on’ the same mass in the collision partner, here F + CF3 → (CF3)′ + (F)′ at a copper surface. The mechanism of knock-on was shown by Scanning Tunnelling Microscopy to involve reversal of the CF3 umbrella as in Walden inversion, with ejection of (F)′ product along the continuation of the F-reagent direction of motion, in collinear reaction.

scholarly journals Approaching the forbidden fruit of reaction dynamics: Aiming reagent at selected impact parameters

2018 ◽  
Vol 4 (10) ◽  
pp. eaau2821 ◽  
Author(s):  
Kelvin Anggara ◽  
Lydie Leung ◽  
Matthew J. Timm ◽  
Zhixin Hu ◽  
John C. Polanyi
Keyword(s):  
Impact Parameter ◽  
Reaction Dynamics ◽  
Bimolecular Reaction ◽  
Important Variable ◽  
Scanning Tunneling ◽  
Tunneling Microscopy ◽  
Stationary Target ◽  
Impact Parameters ◽  
Miss Distance ◽  
The Impact

Collision geometry is central to reaction dynamics. An important variable in collision geometry is the miss-distance between molecules, known as the “impact parameter.” This is averaged in gas-phase molecular beam studies. By aligning molecules on a surface prior to electron-induced dissociation, we select impact parameters in subsequent inelastic collisions. Surface-collimated “projectile” molecules, difluorocarbene (CF2), were aimed at stationary “target” molecules characterized by scanning tunneling microscopy (STM), with the observed scattering interpreted by computational molecular dynamics. Selection of impact parameters showed that head-on collisions favored bimolecular reaction, whereas glancing collisions led only to momentum transfer. These collimated projectiles could be aimed at the wide variety of adsorbed targets identifiable by STM, with the selected impact parameter assisting in the identification of the collision geometry required for reaction.

Mechanical systems for a synchrotron X-ray-enhanced scanning tunnelling microscope

2010 ◽  
Vol 1 (MEDSI-6) ◽  
Author(s):  
C. Preissner ◽  
V. Rose ◽  
C. Pitts
Keyword(s):  
Vacuum Chamber ◽  
Prototype System ◽  
Scanning Tunnelling Microscope ◽  
X Ray ◽  
Scanning Tunnelling ◽  
Final Design ◽  
Tunnelling Microscopy ◽  
The Impact ◽  
Photon Source

Synchrotron X-ray-enhanced scanning tunnelling microscopy (SXSTM) is a novel technique by which materials can be studied with elemental-sensitive and nanometre-spatial resolution. This poster covers the mechanical engineering design for the prototype SXSTM instrument. System performance and sample handling requirements along with the desire to use existing components constrained the design. The SXSTM needs to be mechanically and acoustically isolated from the environment. In addition, all sample preparations are done in situ, and thus, the sample and SXSTM tips need to be prepared and moved inside the vacuum chamber with a wobble stick. The final design incorporates an Advanced Photon Source-designed vacuum chamber, existing components and commercial parts to provide the user with a robust prototype system to demonstrate the impact of this new technique.

An Improved Method for the Preparation and TEM Examination of Sharp Pointed Tips used in APFIM and STM

1990 ◽  
Vol 48 (2) ◽  
pp. 102-103
Author(s):  
E.A. Fischione ◽  
P.E. Fischione ◽  
J.J. Haugh ◽  
M.G. Burke
Keyword(s):  
Atom Probe ◽  
Preparation Process ◽  
Improved Method ◽  
Ion Milling ◽  
Polishing Process ◽  
Probe Field ◽  
Scanning Tunnelling ◽  
Stm Tips ◽  
Tunnelling Microscopy ◽  
Ion Microscopy

A common requirement for both Atom Probe Field-Ion Microscopy (APFIM) and Scanning Tunnelling Microscopy (STM) is a sharp pointed tip for use as either the specimen (APFIM) or the probe (STM). Traditionally, tips have been prepared by either chemical or electropolishing techniques. Recently, ion-milling has been successfully employed in the production of APFIM tips [1]. Conventional electropolishing techniques are applicable to a wide variety of metals, but generally require careful manual adjustments during the polishing process and may also be time-consuming. In order to reduce the time and effort involved in the preparation process, a compact, self-contained polishing unit has been developed. This system is based upon the conventional two-stage electropolishing technique in which the specimen/tip blank is first locally thinned or “necked”, and subsequently electropolished until separation occurs.[2,3] The result of this process is the production of two APFIM or STM tips. A mechanized polishing unit that provides these functions while automatically maintaining alignment has been designed and developed.

Mechanically-Tunable Quantum Interference in Ferrocene-Based Single-Molecule Junctions

2020 ◽  
Author(s):  
María Camarasa-Gómez ◽  
Daniel Hernangómez-Pérez ◽  
Michael S. Inkpen ◽  
Giacomo Lovat ◽  
E-Dean Fung ◽  
...  
Keyword(s):  
Single Molecule ◽  
Quantum Interference ◽  
Degrees Of Freedom ◽  
Building Blocks ◽  
Ferrocene Derivative ◽  
Single Molecule Junctions ◽  
Molecule Junction ◽  
Single Molecule Junction ◽  
The Impact ◽  
D Orbitals

Ferrocenes are ubiquitous organometallic building blocks that comprise a Fe atom sandwiched between two cyclopentadienyl (Cp) rings that rotate freely at room temperature. Of widespread interest in fundamental studies and real-world applications, they have also attracted<br>some interest as functional elements of molecular-scale devices. Here we investigate the impact of<br>the configurational degrees of freedom of a ferrocene derivative on its single-molecule junction<br>conductance. Measurements indicate that the conductance of the ferrocene derivative, which is<br>suppressed by two orders of magnitude as compared to a fully conjugated analog, can be modulated<br>by altering the junction configuration. Ab initio transport calculations show that the low conductance is a consequence of destructive quantum interference effects that arise from the hybridization of metal-based d-orbitals and the ligand-based π-system. By rotating the Cp rings, the hybridization, and thus the quantum interference, can be mechanically controlled, resulting in a conductance modulation that is seen experimentally.<br>

Biotransformation of Coumarins by Filamentous Fungi: An Alternative Way for Achievement of Bioactive Analogs

2019 ◽  
Vol 16 (6) ◽  
pp. 568-577 ◽  
Author(s):  
Jainara Santos do Nascimento ◽  
João Carlos Silva Conceição ◽  
Eliane de Oliveira Silva
Keyword(s):  
Filamentous Fungi ◽  
Chemical Reactions ◽  
Biological Activities ◽  
Chemical Transformations ◽  
Chemical Structures ◽  
Pattern Structures ◽  
Pharmacological Interest ◽  
Aspergillus Sp ◽  
The Impact ◽  
Related Compounds

Coumarins are natural 1,2-benzopyrones, present in remarkable amounts as secondary metabolites in edible and medicinal plants. The low yield in the coumarins isolation from natural sources, along with the difficulties faced by the total synthesis, make them attractive for biotechnological studies. The current literature contains several reports on the biotransformation of coumarins by fungi, which can generate chemical analogs with high selectivity, using mild and eco-friendly conditions. Prompted by the enormous pharmacological interest in the coumarin-related compounds, their alimentary and chemical applications, this review covers the biotransformation of coumarins by filamentous fungi. The chemical structures of the analogs were presented and compared with those from the pattern structures. The main chemical reactions catalyzed the insertion of functional groups, and the impact on the biological activities caused by the chemical transformations were discussed. Several chemical reactions can be catalyzed by filamentous fungi in the coumarin scores, mainly lactone ring opening, C3-C4 reduction and hydroxylation. Chunninghamella sp. and Aspergillus sp. are the most common fungi used in these transformations. Concerning the substrates, the biotransformation of pyranocoumarins is a rarer process. Sometimes, the bioactivities were improved by the chemical modifications and coincidences with the mammalian metabolism were pointed out.

scholarly journals A note on the relations between elastic and inelastic interactions and increasing ratio σel(s)/σtot(s) at the LHC

2019 ◽  
Vol 34 (32) ◽  
pp. 1950259 ◽  
Author(s):  
S. M. Troshin ◽  
N. E. Tyurin
Keyword(s):  
Elastic Scattering ◽  
Energy Dependence ◽  
Impact Parameter ◽  
Cross Sections ◽  
Parameter Dependence ◽  
Slope Parameter ◽  
Short Notice ◽  
Inelastic Interactions ◽  
The Impact ◽  
Mode A

We comment briefly on relations between the elastic and inelastic cross-sections valid for the shadow and reflective modes of the elastic scattering. Those are based on the unitarity arguments. It is shown that the redistribution of the probabilities of the elastic and inelastic interactions (the form of the inelastic overlap function becomes peripheral) under the reflective scattering mode can lead to increasing ratio of [Formula: see text] at the LHC energies. In the shadow scattering mode, the mechanism of this increase is a different one, since the impact parameter dependence of the inelastic interactions probability is central in this mode. A short notice is also given on the slope parameter and the leading contributions to its energy dependence in both modes.

scholarly journals The halo model as a versatile tool to predict intrinsic alignments

2020 ◽  
Author(s):  
Maria Cristina Fortuna ◽  
Henk Hoekstra ◽  
Benjamin Joachimi ◽  
Harry Johnston ◽  
Nora Elisa Chisari ◽  
...  
Keyword(s):  
Degrees Of Freedom ◽  
Power Spectra ◽  
Stage Iv ◽  
Stage Iii ◽  
Radial Dependence ◽  
Additional Parameter ◽  
Small Scales ◽  
Cosmic Shear ◽  
Galaxy Populations ◽  
The Impact

Abstract Intrinsic alignments (IAs) of galaxies are an important contaminant for cosmic shear studies, but the modelling is complicated by the dependence of the signal on the source galaxy sample. In this paper, we use the halo model formalism to capture this diversity and examine its implications for Stage-III and Stage-IV cosmic shear surveys. We account for the different IA signatures at large and small scales, as well for the different contributions from central/satellite and red/blue galaxies, and we use realistic mocks to account for the characteristics of the galaxy populations as a function of redshift. We inform our model using the most recent observational findings: we include a luminosity dependence at both large and small scales and a radial dependence of the signal within the halo. We predict the impact of the total IA signal on the lensing angular power spectra, including the current uncertainties from the IA best-fits to illustrate the range of possible impact on the lensing signal: the lack of constraints for fainter galaxies is the main source of uncertainty for our predictions of the IA signal. We investigate how well effective models with limited degrees of freedom can account for the complexity of the IA signal. Although these lead to negligible biases for Stage-III surveys, we find that, for Stage-IV surveys, it is essential to at least include an additional parameter to capture the redshift dependence.

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