scholarly journals Controlling the symmetry of inorganic ionic nanofilms with optical chirality

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Christopher Kelly ◽  
Donald A. MacLaren ◽  
Katie McKay ◽  
Anthony McFarlane ◽  
Affar S. Karimullah ◽  
...  

Abstract Manipulating symmetry environments of metal ions to control functional properties is a fundamental concept of chemistry. For example, lattice strain enables control of symmetry in solids through a change in the nuclear positions surrounding a metal centre. Light–matter interactions can also induce strain but providing dynamic symmetry control is restricted to specific materials under intense laser illumination. Here, we show how effective chemical symmetry can be tuned by creating a symmetry-breaking rotational bulk polarisation in the electronic charge distribution surrounding a metal centre, which we term a meta-crystal field. The effect arises from an interface-mediated transfer of optical spin from a chiral light beam to produce an electronic torque that replicates the effect of strain created by high pressures. Since the phenomenon does not rely on a physical rearrangement of nuclear positions, material constraints are lifted, thus providing a generic and fully reversible method of manipulating effective symmetry in solids.

2017 ◽  
Vol 197 ◽  
pp. 505-516 ◽  
Author(s):  
Jenny Schneider ◽  
Konstantin Nikitin ◽  
Ralf Dillert ◽  
Detlef W. Bahnemann

Herein, we report the effect of the laser illumination during the diffuse-reflectance laser-flash-photolysis measurements on the morphological and optical properties of TiO2 powders. A grey-blue coloration of the TiO2 nanoparticles has been observed after intense laser illumination. This is explained by the formation of nonreactive trapped electrons accompanied by the release of oxygen atoms from the TiO2 matrix as detected by means of UV-vis and EPR spectroscopy. Moreover, in the case of the pure anatase sample a phase transition of some TiO2 nanoparticles located in the inner region from anatase to rutile occurred. It is suggested that these structural changes in TiO2 are caused by an energy and charge transfer to the TiO2 lattice.


1997 ◽  
Vol 3 (3) ◽  
pp. 214-223 ◽  
Author(s):  
Jon C. Lovegren ◽  
Gail A. Massey

Abstract: Interactions among discrete charges in the emission current of a photoelectron imaging system can limit its spatial resolution, significantly affecting the performance and design of emission microscopes employing high current densities. Under intense laser illumination a sample can emit photocurrent densities exceeding tens of amperes/cm2. This study describes Monte Carlo estimations of electron trajectory aberrations produced by discrete electron space charge interactions in a photoelectron emission microscope. The results also apply to photoelectron sources that might be used in other kinds of devices. A model of the emission process was used to assemble bunches of about 500 randomly positioned electrons whose individual trajectories were computed. Trajectory distortions of one member in each bunch that were due to the coulomb forces exerted by its neighbors were used to evaluate aberrations for a variety of voltages, current densities, and instrument configurations. Aberrations estimated in this way are smaller than those predicted by earlier theory or obtained in pulsed imaging experiments. Here we discuss the reasons for these differences, offer suggestions for improved instruments, and present experimental images.


Author(s):  
Lluís Artús Suàrez ◽  
David Balcells ◽  
Ainara Nova

AbstractThe deaminative hydrogenation of amides is one of the most convenient pathways for the synthesis of amines and alcohols. The ideal source of reducing equivalents for this reaction is molecular hydrogen, though, in practice, this approach requires high pressures and temperatures, with many catalysts achieving only small turnover numbers and frequencies. Nonetheless, during the last ten years, this field has made major advances towards larger turnovers under milder conditions thanks to the development of bifunctional catalysts. These systems promote the heterolytic cleavage of hydrogen into proton and hydride by combining a basic ligand with an acidic metal centre. The present review focuses on the computational study of the reaction mechanism underlying bifunctional catalysis. This review is structured around the fundamental steps of this mechanism, namely the C=O and C–N hydrogenation of the amide, the C–N protonolysis of the hemiaminal, the C=O hydrogenation of the aldehyde, and the competition between hydrogen activation and catalyst deactivation. In line with the complexity of the mechanism, we also provide a perspective on the use of microkinetic models. Both Noyori- and Milstein-type catalysts are discussed and compared.


Author(s):  
J. Barbillat ◽  
M. Delhaye ◽  
P. Dhamelincourt

Raman mapping, with a spatial resolution close to the diffraction limit, can help to reveal the distribution of chemical species at the surface of an heterogeneous sample.As early as 1975,three methods of sample laser illumination and detector configuration have been proposed to perform Raman mapping at the microscopic level (Fig. 1),:- Point illumination:The basic design of the instrument is a classical Raman microprobe equipped with a PM tube or either a linear photodiode array or a two-dimensional CCD detector. A laser beam is focused on a very small area ,close to the diffraction limit.In order to explore the whole surface of the sample,the specimen is moved sequentially beneath the microscope by means of a motorized XY stage. For each point analyzed, a complete spectrum is obtained from which spectral information of interest is extracted for Raman image reconstruction.- Line illuminationA narrow laser line is focused onto the sample either by a cylindrical lens or by a scanning device and is optically conjugated with the entrance slit of the stigmatic spectrograph.


Author(s):  
C. J. Joachain ◽  
N. J. Kylstra ◽  
R. M. Potvliege

1998 ◽  
Vol 77 (4) ◽  
pp. 1063-1075
Author(s):  
W. C. Mackrodt, E.-A. Williamson, D. W

Author(s):  
Van B. Nakagawara ◽  
Ronald W. Montgomery ◽  
Archie E. Dillard ◽  
Leon N. McLin ◽  
C. William Connor

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