Competitive Chloride Chemisorption Disrupts Hydrogen Bonding Networks: DFT, Crystallography, Thermodynamics, and Morphological Consequences

CORROSION ◽  
10.5006/2555 ◽  
2017 ◽  
Vol 74 (3) ◽  
pp. 295-311 ◽  
Author(s):  
Laurence Marks
Keyword(s):  
Hydrogen Bonding ◽  
Surface Science ◽  
Density Functional ◽  
Chloride Ions ◽  
Oxide Surface ◽  
Aqueous Environment ◽  
Aqueous Corrosion ◽  
Function Change ◽  
Competing Models ◽  
Galvanic Couples

The consequence for aqueous corrosion of chloride ions in an aqueous environment on the surface structure and thermodynamics of hydroxylated magnesia (001) and alpha-alumina (001) and (100) is analyzed using density functional methods. It is shown that there is competitive chemisorption between hydroxide and chloride, with the chloride disrupting the hydrogen bonding network on the surface. There is a significant crystallographic dependence, as well as dependencies upon the environment in terms of the pH and chloride molarity. An analysis of the results in terms of existing, competing models in the literature for the effect of chloride indicates that rather than the existing models being competitors, most are correct but incomplete. Rather than the different models being viewed as competitors, or each being rate determining for some specific set of conditions, the majority are simultaneously correct. Conventional oxide surface science extrapolation of the results yields qualitative conclusions for the effects of, for instance, alloy dopants which are consistent with existing experimental data. The analysis also indicates the existence of a number of new phenomena in corrosion, for instance local galvanic couples due to the work-function change with chloride chemisorption, as well as thermodynamic dewetting of the oxide film.

scholarly journals NMR of Natural Products as Potential Drugs

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3763
Author(s):  
Poul Erik Hansen
Keyword(s):  
Natural Products ◽  
Hydrogen Bonding ◽  
Density Functional ◽  
Chemical Shifts ◽  
Isotope Effects ◽  
Density Functional Theory Calculations ◽  
Intramolecular Hydrogen Bonding ◽  
Chemical Equilibria ◽  
Nmr Techniques ◽  
Intramolecular Hydrogen

This review outlines methods to investigate the structure of natural products with emphasis on intramolecular hydrogen bonding, tautomerism and ionic structures using NMR techniques. The focus is on 1H chemical shifts, isotope effects on chemical shifts and diffusion ordered spectroscopy. In addition, density functional theory calculations are performed to support NMR results. The review demonstrates how hydrogen bonding may lead to specific structures and how chemical equilibria, as well as tautomeric equilibria and ionic structures, can be detected. All these features are important for biological activity and a prerequisite for correct docking experiments and future use as drugs.

scholarly journals One-Dimensional Organic–Inorganic Material (C6H9N2)2BiCl5: From Synthesis to Structural, Spectroscopic, and Electronic Characterizations

2021 ◽  
Vol 22 (4) ◽  
pp. 2030
Author(s):  
Hela Ferjani ◽  
Hammouda Chebbi ◽  
Mohammed Fettouhi
Keyword(s):  
Hydrogen Bonding ◽  
Density Functional ◽  
Crystal Packing ◽  
Diffuse Reflectance Spectrum ◽  
Enrichment Ratio ◽  
One Dimensional ◽  
Organic Part ◽  
Fukui Indices ◽  
The Stability ◽  
The One

The new organic–inorganic compound (C6H9N2)2BiCl5 (I) has been grown by the solvent evaporation method. The one-dimensional (1D) structure of the allylimidazolium chlorobismuthate (I) has been determined by single crystal X-ray diffraction. It crystallizes in the centrosymmetric space group C2/c and consists of 1-allylimidazolium cations and (1D) chains of the anion BiCl52−, built up of corner-sharing [BiCl63−] octahedra which are interconnected by means of hydrogen bonding contacts N/C–H⋯Cl. The intermolecular interactions were quantified using Hirshfeld surface analysis and the enrichment ratio established that the most important role in the stability of the crystal structure was provided by hydrogen bonding and H···H interactions. The highest value of E was calculated for the contact N⋯C (6.87) followed by C⋯C (2.85) and Bi⋯Cl (2.43). These contacts were favored and made the main contribution to the crystal packing. The vibrational modes were identified and assigned by infrared and Raman spectroscopy. The optical band gap (Eg = 3.26 eV) was calculated from the diffuse reflectance spectrum and showed that we can consider the material as a semiconductor. The density functional theory (DFT) has been used to determine the calculated gap, which was about 3.73 eV, and to explain the electronic structure of the title compound, its optical properties, and the stability of the organic part by the calculation of HOMO and LUMO energy and the Fukui indices.

scholarly journals Theoretical Study of the Structures of 4-(2,3,5,6-Tetrafluoropyridyl)Diphenylphosphine Oxide and Tris(Pentafluorophenyl)Phosphine Oxide: Why Does the Crystal Structure of (Tetrafluoropyridyl)Diphenylphosphine Oxide Have Two Different P=O Bond Lengths?

Molecules ◽  
2020 ◽  
Vol 25 (12) ◽  
pp. 2778
Author(s):  
Joseph R. Lane ◽  
Graham C. Saunders
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Phosphine Oxide ◽  
Density Functional ◽  
Lone Pair ◽  
Diphenylphosphine Oxide ◽  
Functional Theory ◽  
Weak Hydrogen Bonding ◽  
Independent Molecules ◽  
The Difference

The crystal structure of 4-(2,3,5,6-tetrafluoropyridyl)diphenylphosphine oxide (1) contains two independent molecules in the asymmetric unit. Although the molecules are virtually identical in all other aspects, the P=O bond distances differ by ca. 0.02 Å. In contrast, although tris(pentafluorophenyl)phosphine oxide (2) has a similar crystal structure, the P=O bond distances of the two independent molecules are identical. To investigate the reason for the difference, a density functional theory study was undertaken. Both structures comprise chains of molecules. The attraction between molecules of 1, which comprises lone pair–π, weak hydrogen bonding and C–H∙∙∙arene interactions, has energies of 70 and 71 kJ mol−1. The attraction between molecules of 2 comprises two lone pair–π interactions, and has energies of 99 and 100 kJ mol−1. There is weak hydrogen bonding between molecules of adjacent chains involving the oxygen atom of 1. For one molecule, this interaction is with a symmetry independent molecule, whereas for the other, it also occurs with a symmetry related molecule. This provides a reason for the difference in P=O distance. This interaction is not possible for 2, and so there is no difference between the P=O distances of 2.

Chemical Effects at the Reaction Front in Corroding Spent Nuclear Fuel

2006 ◽  
Vol 985 ◽  
Author(s):  
Jeffrey A. Fortner ◽  
A. Jeremy Kropf ◽  
James L. Jerden ◽  
James C. Cunnane
Keyword(s):  
Transition Zone ◽  
Nuclear Fuel ◽  
Spent Nuclear Fuel ◽  
Aqueous Environment ◽  
Spent Fuel ◽  
Aqueous Corrosion ◽  
Reduction Potentials ◽  
Chemical Effects ◽  
Before And After ◽  
X Ray Absorption

AbstractPerformance assessment models of the U. S. repository at Yucca Mountain, Nevada suggest that neptunium from spent nuclear fuel is a potentially important dose contributor. A scientific understanding of how the UO2 matrix of spent nuclear fuel impacts the oxidative dissolution and reductive precipitation of Np is needed to predict the behavior of Np at the fuel surface during aqueous corrosion. Neptunium would most likely be transported as aqueous Np(V) species, but for this to occur it must first be oxidized from the Np(IV) state found within the parent spent nuclear fuel. In this paper we present synchrotron x-ray absorption spectroscopy and microscopy findings that illuminate the resultant local chemistry of neptunium and plutonium within uranium oxide spent nuclear fuel before and after corrosive alteration in an air-saturated aqueous environment. We find the Pu and Np in unaltered spent fuel to have a +4 oxidation state and an environment consistent with solid-solution in the UO2 matrix. During corrosion in an air-saturated aqueous environment, the uranium matrix is converted to uranyl (UO22+) mineral assemblage that is depleted in Np and Pu relative to the parent fuel. The transition from U(IV) in the fuel to a fully U(VI) character across the corrosion front is not sharp, but occurs over a transition zone of ∼ 50 micrometers. We find evidence of a thin (∼ 20 micrometer) layer that is enriched in Pu and Np within a predominantly U(IV) environment on the fuel side of the transition zone. These experimental observations are consistent with available data for the standard reduction potentials for NpO2+/Np4+ and UO22+/U4+ couples, which indicate that Np(IV) may not be effectively oxidized to Np(V) at the corrosion potential of uranium dioxide spent nuclear fuel in air-saturated aqueous solutions.

scholarly journals AlO6 clusters’ electric storage effect in amorphous alumina supercapacitors

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Mikio Fukuhara ◽  
Tomoyuki Kuroda ◽  
Fumihiko Hasegawa ◽  
Toshiyuki Hashida ◽  
Mitsuhiro Takeda ◽  
...  
Keyword(s):  
Electron Beam ◽  
Coulomb Blockade ◽  
Density Functional ◽  
Electron Beam Irradiation ◽  
Oxide Surface ◽  
Storage Effect ◽  
Beam Irradiation ◽  
Original Length ◽  
Ragone Plot ◽  
Amorphous Alumina

AbstractIn this study, the electric storage effect of AlO6 clusters in amorphous alumina (AAO) supercapacitors was investigated in terms of cluster morphologies under electron-beam irradiation. Based on first-principles density functional calculation, the optimised structure of AlO6 clusters around an O-vacancy is characterised by a large vacant space created by the absence of an O atom and its neighbouring Al atom. The localised electrons present near the two-atomic vacancies induce positive charges on the inside of the insulating oxide surface, ensuring the adsorption of many electrons on the surface. Electron-beam irradiation (adsorption) from 100 to 180 keV causes the lengths of the Al–O bonds of the cluster to shrink, but then return to the original length with decreasing voltage energy, indicating a rocking-chair-type charge-breathing effect accompanied by a volume expansion of approximately 4%. The I–V and I–R characteristics depicted Coulomb blockade for the switching effect of both the negative and positive potentials. The Ragone plot of the AAO supercapacitor is located at capability area of the second cell.

CAN SEMIEMPIRICAL QUANTUM MODELS CALCULATE THE BINDING ENERGY OF HYDROGEN BONDING FOR BIOLOGICAL SYSTEMS?

2009 ◽  
Vol 08 (04) ◽  
pp. 691-711 ◽  
Author(s):  
FENG FENG ◽  
HUAN WANG ◽  
WEI-HAI FANG ◽  
JIAN-GUO YU
Keyword(s):  
Hydrogen Bonding ◽  
Amino Acid ◽  
Amino Acid Residue ◽  
Density Functional ◽  
Biological Systems ◽  
Binding Energies ◽  
Semiempirical Model ◽  
Hydrogen Bonded Systems ◽  
High Level ◽  
Hydrogen Bonded

A modified semiempirical model named RM1BH, which is based on RM1 parameterizations, is proposed to simulate varied biological hydrogen-bonded systems. The RM1BH is formulated by adding Gaussian functions to the core–core repulsion items in original RM1 formula to reproduce the binding energies of hydrogen bonding of experimental and high-level computational results. In the parameterizations of our new model, 35 base-pair dimers, 18 amino acid residue dimers, 14 dimers between a base and an amino acid residue, and 20 other multimers were included. The results performed with RM1BH were compared with experimental values and the benchmark density-functional (B3LYP/6-31G**/BSSE) and Möller–Plesset perturbation (MP2/6-31G**/BSSE) calculations on various biological hydrogen-bonded systems. It was demonstrated that RM1BH model outperforms the PM3 and RM1 models in the calculations of the binding energies of biological hydrogen-bonded systems by very close agreement with the values of both high-level calculations and experiments. These results provide insight into the ideas, methods, and views of semiempirical modifications to investigate the weak interactions of biological systems.

scholarly journals Density functional theory study with and without COSMO of H2 SO4 reactions in an aqueous environment for metal extraction

2018 ◽  
Vol 40 (3) ◽  
pp. 591-606 ◽  
Author(s):  
Maria Johanna Ungerer ◽  
Cornelia Gertina Catharina Elizabet van Sittert ◽  
Derik Johannes van der Westhuizen ◽  
Henning Manfred Krieg
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Metal Extraction ◽  
Aqueous Environment ◽  
Density Functional Theory Study ◽  
Functional Theory
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