scholarly journals Electronic Effects At Interfaces In Cu (cr, mo, w, ta, re) Multilayers

1998 ◽  
Vol 524 ◽  
Author(s):  
A. F. Bello ◽  
T. Van Buuren ◽  
J. E. Klepeis ◽  
T. W. Barbee
Keyword(s):  
Charge Transfer ◽  
Transition Metal ◽  
Metallic Multilayers ◽  
Electronic Effects ◽  
White Line ◽  
Enhanced Absorption ◽  
Absorption Energy ◽  
A Charge ◽  
X Ray Absorption ◽  
Metal Layers

ABSTRACTInterfacial electronic effects between Cu and the transition metals Cr, Mo, W, Ta, Re, are investigated by determining the strength of the white line absorption resonances on the L3,2 edges of Cu in Cu5/TM5 multilayers. X-ray absorption (XAS) was performed to study the white lines, which are directly related to the unoccupied states of Cu in the multilayers. The metallic multilayers are 2 nm in period and 200 nm in total thickness. Each period contains 5 monolayers of Cu and 5 monolayers of the transition metal: = 40% of the atoms are at interfaces. These material pairs form ideal structures for the investigation of interfacial electronic effects as they form no compounds and exhibit terminal solid solubility. Only weak white lines are observed on the L3,2 edges of Cu since all the d-orbitals are filled. In the Cu/TM multilayers, however, we observed enhancement of the Cu white lines. We attribute this to the charge transfer from the “interfacial Cu atoms” d-orbital to the transition metal layers. Analysis of the white line enhancement enables calculation of the charge transfer calculation from the Cu to the transition metal. Cu shows a charge transfer of about 0.03 electrons/interfacial Cu atom in Cu/Cr, 0.064 in Cu/Mo, 0.35 in Cu/Ta, 0.17 in Cu/W , and 0.23 in Cu/Re. This charge transfer is consistent with the enhanced absorption energy of Cu on these materials as observed in thermal desorption experiments.

scholarly journals Defect passivation of transition metal dichalcogenides via a charge transfer van der Waals interface

2017 ◽  
Vol 3 (10) ◽  
pp. e1701661 ◽  
Author(s):  
Jun Hong Park ◽  
Atresh Sanne ◽  
Yuzheng Guo ◽  
Matin Amani ◽  
Kehao Zhang ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Transition Metal ◽  
Van Der Waals ◽  
Transition Metal Dichalcogenides ◽  
Defect Passivation ◽  
Metal Dichalcogenides ◽  
A Charge

scholarly journals Halogen Bonding Involving I2 and d8 Transition-Metal Pincer Complexes

Crystals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 373
Author(s):  
Marek Freindorf ◽  
Seth Yannacone ◽  
Vytor Oliveira ◽  
Niraj Verma ◽  
Elfi Kraka
Keyword(s):  
Charge Transfer ◽  
Transition Metal ◽  
Bond Strength ◽  
Oxidative Addition ◽  
Halogen Bonding ◽  
Mode Analysis ◽  
Pincer Complexes ◽  
Local Mode ◽  
Electronic Effects ◽  
Pincer Complex

We systematically investigated iodine–metal and iodine–iodine bonding in van Koten’s pincer complex and 19 modifications changing substituents and/or the transition metal with a PBE0–D3(BJ)/aug–cc–pVTZ/PP(M,I) model chemistry. As a novel tool for the quantitative assessment of the iodine–metal and iodine–iodine bond strength in these complexes we used the local mode analysis, originally introduced by Konkoli and Cremer, complemented with NBO and Bader’s QTAIM analyses. Our study reveals the major electronic effects in the catalytic activity of the M–I–I non-classical three-center bond of the pincer complex, which is involved in the oxidative addition of molecular iodine I2 to the metal center. According to our investigations the charge transfer from the metal to the σ* antibonding orbital of the I–I bond changes the 3c–4e character of the M–I–I three-center bond, which leads to weakening of the iodine I–I bond and strengthening of the metal–iodine M–I bond, facilitating in this way the oxidative addition of I2 to the metal. The charge transfer can be systematically modified by substitution at different places of the pincer complex and by different transition metals, changing the strength of both the M–I and the I2 bonds. We also modeled for the original pincer complex how solvents with different polarity influence the 3c–4e character of the M–I–I bond. Our results provide new guidelines for the design of pincer complexes with specific iodine–metal bond strengths and introduce the local vibrational mode analysis as an efficient tool to assess the bond strength in complexes.

EELS white line intensities calculated for the 3d and 4d metals

1989 ◽  
Vol 47 ◽  
pp. 388-389
Author(s):  
C. C. Ahn ◽  
D. H. Pearson ◽  
P. Rez ◽  
B. Fultz
Keyword(s):  
Experimental Data ◽  
Line Intensity ◽  
Transition Probabilities ◽  
Initial Increase ◽  
White Line ◽  
Hartree Fock ◽  
Line Intensities ◽  
Integrated Intensity ◽  
X Ray Absorption ◽  
The Continuum

Previous experimental measurements of the total white line intensities from L2,3 energy loss spectra of 3d transition metals reported a linear dependence of the white line intensity on 3d occupancy. These results are inconsistent, however, with behavior inferred from relativistic one electron Dirac-Fock calculations, which show an initial increase followed by a decrease of total white line intensity across the 3d series. This inconsistency with experimental data is especially puzzling in light of work by Thole, et al., which successfully calculates x-ray absorption spectra of the lanthanide M4,5 white lines by employing a less rigorous Hartree-Fock calculation with relativistic corrections based on the work of Cowan. When restricted to transitions allowed by dipole selection rules, the calculated spectra of the lanthanide M4,5 white lines show a decreasing intensity as a function of Z that was consistent with the available experimental data.Here we report the results of Dirac-Fock calculations of the L2,3 white lines of the 3d and 4d elements, and compare the results to the experimental work of Pearson et al. In a previous study, similar calculations helped to account for the non-statistical behavior of L3/L2 ratios of the 3d metals. We assumed that all metals had a single 4s electron. Because these calculations provide absolute transition probabilities, to compare the calculated white line intensities to the experimental data, we normalized the calculated intensities to the intensity of the continuum above the L3 edges. The continuum intensity was obtained by Hartree-Slater calculations, and the normalization factor for the white line intensities was the integrated intensity in an energy window of fixed width and position above the L3 edge of each element.

Determination of Epsilon Aminocaproic Acid Based on Charge Transfer Complexation with p-Nitrophenlol by Spectrophotometry

2020 ◽  
Vol 16 ◽  
Author(s):  
Sheng-Yun Li ◽  
Fang Tian
Keyword(s):  
Charge Transfer ◽  
Aminocaproic Acid ◽  
Concentration Limit ◽  
Official Method ◽  
Good Precision ◽  
Pharmaceutical Dosage Forms ◽  
Relative Standard ◽  
A Charge ◽  
Epsilon Aminocaproic Acid

: A spectrophotometry was investigated for the determination of epsilon aminocaproic acid (EACA) with p-nitrophenol (PNP). The method was based on a charge transfer (CT) complexation of this drug as n-electron donor with π-acceptor PNP. Experiment indicated that the CT complexation was carried out at room temperature for 10 minutes in dimethyl sulfoxide solvent. The spectrum obtained for EACA/PNP system showed the maximum absorption band at wavelength of 425 nm. The stoichiometry of the CT complex was found to be 1:1 ratio by Job’s method between the donor and the acceptor. Different variables affecting the complexation were carefully studied and optimized. At the optimum reaction conditions, Beer’s law was obeyed in a concentration limit of 1～6 µg mL-1. The relative standard deviation was less than 2.9%. The apparent molar absoptivity was determined to be 1.86×104 L mol-1cm-1 at 425 nm. The CT complexation was also confirmed by both FTIR and 1H NMR measurements. The thermodynamic properties and reaction mechanism of the CT complexation have been discussed. The developed method could be applied successfully for the determination of the studied compound in its pharmaceutical dosage forms with a good precision and accuracy compared to official method as revealed by t- and F-tests.

Fluorescence Quenching of Aminodiphenylamines with Chloromethanes

2002 ◽  
Vol 67 (8) ◽  
pp. 1154-1164 ◽  
Author(s):  
Nachiappan Radha ◽  
Meenakshisundaram Swaminathan
Keyword(s):  
Charge Transfer ◽  
Fluorescence Quenching ◽  
Ground State ◽  
Rate Constants ◽  
Quenching Mechanism ◽  
Quenching Rate ◽  
Charge Transfer Interaction ◽  
Electronically Excited ◽  
A Charge

The fluorescence quenching of 2-aminodiphenylamine (2ADPA), 4-aminodiphenylamine (4ADPA) and 4,4'-diaminodiphenylamine (DADPA) with tetrachloromethane, chloroform and dichloromethane have been studied in hexane, dioxane, acetonitrile and methanol as solvents. The quenching rate constants for the process have also been obtained by measuring the lifetimes of the fluorophores. The quenching was found to be dynamic in all cases. For 2ADPA and 4ADPA, the quenching rate constants of CCl4 and CHCl3 depend on the viscosity, whereas in the case of CH2Cl2, kq depends on polarity. The quenching rate constants for DADPA with CCl4 are viscosity-dependent but the quenching with CHCl3 and CH2Cl2 depends on the polarity of the solvents. From the results, the quenching mechanism is explained by the formation of a non-emissive complex involving a charge-transfer interaction between the electronically excited fluorophores and ground-state chloromethanes.

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