A DFT study of spherands containing five anisyl groups — Highly preorganized to bind the alkali metal

2006 ◽  
Vol 84 (8) ◽  
pp. 1045-1049 ◽  
Author(s):  
Shabaan AK Elroby ◽  
Kyu Hwan Lee ◽  
Seung Joo Cho ◽  
Alan Hinchliffe
Keyword(s):  
Density Functional Theory ◽  
Binding Energy ◽  
Density Functional ◽  
Ionic Radius ◽  
Binding Energies ◽  
Cavity Size ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Good Agreement

Although anisyl units are basically poor ligands for metal ions, the rigid placements of their oxygens during synthesis rather than during complexation are undoubtedly responsible for the enhanced binding and selectivity of the spherand. We used standard B3LYP/6-31G** (5d) density functional theory (DFT) to investigate the complexation between spherands containing five anisyl groups, with CH2–O–CH2 (2) and CH2–S–CH2 (3) units in an 18-membered macrocyclic ring, and the cationic guests (Li+, Na+, and K+). Our geometric structure results for spherands 1, 2, and 3 are in good agreement with the previously reported X-ray diffraction data. The absolute values of the binding energy of all the spherands are inversely proportional to the ionic radius of the guests. The results, taken as a whole, show that replacement of one anisyl group by CH2–O–CH2 (2) and CH2–S–CH2 (3) makes the cavity bigger and less preorganized. In addition, both the binding and specificity decrease for small ions. The spherands 2 and 3 appear beautifully preorganized to bind all guests, so it is not surprising that their binding energies are close to the parent spherand 1. Interestingly, there is a clear linear relation between the radius of the cavity and the binding energy (R2 = 0.999).Key words: spherands, preorganization, density functional theory, binding energy, cavity size.

scholarly journals Effects in the Optical and Structural Properties Caused by Mg or Zn Doping of GaN Films Grown via Radio-Frequency Magnetron Sputtering Using Laboratory-Prepared Targets

2021 ◽  
Vol 11 (15) ◽  
pp. 6990
Author(s):  
Erick Gastellóu ◽  
Godofredo García ◽  
Ana María Herrera ◽  
Crisoforo Morales ◽  
Rafael García ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Magnetron Sputtering ◽  
Radio Frequency ◽  
Hexagonal Structure ◽  
Binding Energies ◽  
Radio Frequency Magnetron ◽  
Radio Frequency Magnetron Sputtering ◽  
X Ray ◽  
Diffraction Patterns ◽  
Mg Doped

GaN films doped with Mg or Zn were obtained via radio-frequency magnetron sputtering on silicon substrates at room temperature and used laboratory-prepared targets with Mg-doped or Zn-doped GaN powders. X-ray diffraction patterns showed broadening peaks, which could have been related to the appearance of nano-crystallites with an average of 7 nm. Scanning electron microscopy and transmission electron microscopy showed good adherence to silicon non-native substrate, as well as homogeneity, with a grain size average of 0.14 µm, and 0.16 µm for the GaN films doped with Zn or Mg, respectively. X-ray photo-electron spectroscopy demonstrated the presence of a very small amount of magnesium (2.10 mol%), and zinc (1.15 mol%) with binding energies of 1303.18, and 1024.76 eV, respectively. Photoluminescence spectrum for the Zn-doped GaN films had an emission range from 2.89 to 3.0 eV (429.23–413.50 nm), while Mg-doped GaN films had an energy emission in a blue-violet band with a range from 2.80 to 3.16 eV (443.03–392.56 nm). Raman spectra showed the classical vibration modes A1(TO), E1(TO), and E2(High) for the hexagonal structure of GaN.

Characterizing the Thermomechanical Degradation of a Filled Elastomer by Morphology and X Ray Photoelectron Spectroscopy

2001 ◽  
Vol 702 ◽  
Author(s):  
Giovanni F Crosta ◽  
Art J Nelson ◽  
Marina C Camatini
Keyword(s):  
Photoelectron Spectroscopy ◽  
Intrinsic Property ◽  
Binding Energies ◽  
Structural Domain ◽  
X Ray ◽  
Vulcanized Rubber ◽  
A Value ◽  
Debris Particles ◽  
Morphological Descriptor ◽  
Microscopy Images

ABSTRACTThree types of debris particles, denoted by L2, H2 and K3 respectively, originated from the abrasion of silica-filled, vulcanized rubber under different test conditions (severity) were analyzed and compared. The structural fractal dimension, DFS, of the particle perimeter was chosen as a morphological descriptor (but not necessarily as an intrinsic property of the fractured material !). Said dimension was estimated by processing light microscopy images. A value of the morphological threshold, TST, which separates the textural from the structural domain in the RICHARDSON plot was determined in order to maximize discrimination between the three particle types and rank them by increasing values of DFS. Particles from the highest severity test (K3) exhibited the highest value of DFS. X ray photoelectron spectroscopy (XPS) provided elemental composition, core level binding energies and the speciation of C, N, O, Si and S. As a result, L2 debris was found to originate from two processes: fracture of rubber and segregation of extender oil. Evidence has come both from morphology and XPS. Particles of H2 and K3 were ascribed to fracture alone. Comparison between K3 and the reference material, rasped rubber (RAS), shows the following: a) increase of the [S]/[C] surface atomic concentration ratio from RAS to K3; b) existence of multiple bonding states of S in K3 with energy peaking at 162.9 ± 0.3 eV ([-S-S-]n); c) weak contribution of R-S-O-R oxidized S species in K3 at 165 eV, not seen in RAS; d) no evidence of either SO3 or SO4 groups in any material. Although preliminary, these results prove the ability of morphological analysis and XPS to characterize the surface properties of debris particles non destructively.

Electronic structure modification in Fe substituted β-Ga2O3 from resonant photoemission and soft x-ray absotption spectroscopies

2021 ◽  
Author(s):  
Sahadeb Ghosh ◽  
Mangala Nand ◽  
Rajiv Kamparath ◽  
Mukul Gupta ◽  
Devdatta M Phase ◽  
...  
Keyword(s):  
Thin Films ◽  
Photoelectron Spectroscopy ◽  
Rf Magnetron Sputtering ◽  
Binding Energies ◽  
Transfer System ◽  
Structure Modification ◽  
X Ray ◽  
Resonant Photoemission ◽  
A Charge ◽  
Fe Substitution

Abstract Oriented thin films of β-(Ga1-xFex)2O3 have been deposited by RF magnetron sputtering on c-Al2O3 and GaN substrates. The itinerant character of Fe 3d states forming the top of the valence band (VB) of Fe substituted of β-Ga2O3 thin films has been determined from resonant photoelectron spectroscopy (RPES). Further, admixture of itinerant and localized character of these Fe 3d sates is obtained for larger binding energies i.e deeper of VB. The bottom of the conduction band (CB) for β-(Ga1-xFex)2O3 is also found to be strongly hybridized states involving Fe 3d and O 2p states as compared to that of Ga 4s in pristine β-Ga2O3. This suggests that β-Ga2O3 transforms from band like system to a charge transfer system with Fe substitution. Furthermore, the bandgap red shits with Fe composition, which has been found to be primarily related to the shift of the CB edge.

scholarly journals Synthesis of new Ln4(Al2O6F2)O2 (Ln = Sm, Eu, Gd) phases with a cuspidine-related structure

IUCrJ ◽  
2019 ◽  
Vol 6 (1) ◽  
pp. 128-135 ◽  
Author(s):  
Aroa Morán-Ruiz ◽  
Aritza Wain-Martin ◽  
Alodia Orera ◽  
María Luisa Sanjuán ◽  
Aitor Larrañaga ◽  
...  
Keyword(s):  
Rare Earth ◽  
Low Temperature ◽  
Raman Spectra ◽  
Photoelectron Spectroscopy ◽  
Binding Energies ◽  
Temperature Reaction ◽  
Rietveld Refinements ◽  
X Ray ◽  
Vinylidene Difluoride ◽  
Vacant Position

The first fluorination of the cuspidine-related phases of Ln4(Al2O7□)O2 (where Ln = Sm, Eu, Gd) is reported. A low-temperature reaction with poly(vinylidene difluoride) lead to the fluorine being substituted in place of oxygen and inserted into the vacant position between the dialuminate groups. X-ray photoelectron spectroscopy shows the presence of the F 1s photoelectron together with an increase in Al 2p and rare-earth 4d binding energies supporting F incorporation. Energy-dispersive X-ray spectroscopy analyses are consistent with the formula Ln4(Al2O6F2)O2, confirming that substitution of one oxygen by two fluoride atoms has been achieved. Rietveld refinements show an expansion in the cell upon fluorination and confirm that the incorporation of fluoride in the Ln4(Al2O7□)O2 structure results in changes in Al coordination from four to five. Thus, the isolated tetrahedral dialuminate Al2O7 groups are converted to chains of distorted square-based pyramids. These structural results are also discussed based on Raman spectra.

scholarly journals On the prediction of core level binding energies in molecules, surfaces and solids

2018 ◽  
Vol 20 (13) ◽  
pp. 8403-8410 ◽  
Author(s):  
Francesc Viñes ◽  
Carmen Sousa ◽  
Francesc Illas
Keyword(s):  
Photoelectron Spectroscopy ◽  
State Of The Art ◽  
Binding Energies ◽  
Core Level ◽  
Chemical Environment ◽  
X Ray ◽  
Unique Information

Core level binding energies, measured by X-ray photoelectron spectroscopy providing unique information regarding the chemical environment of atoms in a system, can be estimated by a diversity of state-of-the-art accurate methods here detailed.

Determination of the oxidation state of manganese in lepidolite by X-ray photoelectron spectroscopy

Clay Minerals ◽  
1982 ◽  
Vol 17 (4) ◽  
pp. 477-481 ◽  
Author(s):  
S. Evans ◽  
E. Raftery
Keyword(s):  
Oxidation State ◽  
Photoelectron Spectroscopy ◽  
Electronic Spectroscopy ◽  
Binding Energies ◽  
Core Electron ◽  
X Ray ◽  
Occasional Occurrence ◽  
The Subject ◽  
Electron Binding Energies

It is usually assumed that the oxidation state of the small proportion of Mn sometimes present in micas is +2, although there is evidence from electronic spectroscopy (Burns, 1970) for at least the occasional occurrence of Mn(III) in manganophyllite. We describe here X-ray photoelectron spectroscopic (XPS) measurements on the Mn in a Norwegian lepidolite which was the subject of a concurrent structural study by X-ray photoelectron diffraction (Evans & Raftery, 1982). To establish the Mn oxidation state we have compared the Mn2p core-electron binding energies (BE), the Mn2P3/2-O ls BE differences, and the Mn2p XPS peak profiles from the four common oxides of manganese (MnO, Mn3O4, Mn2O3 and MnO2) with those from the lepidolite. A re-examination of these oxides was undertaken because the agreement between reports in the literature was unsatisfactory, and uncertainty existed concerning the integrity of some of the surfaces previously examined.

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