Skeletal Transformation of Isolated Pentagon Rule (IPR) Fullerene C82 into Non-IPR C82Cl28 with Notably Low Activation Barriers

2012 ◽  
Vol 51 (21) ◽  
pp. 11226-11228 ◽  
Author(s):  
Ilya N. Ioffe ◽  
Olga N. Mazaleva ◽  
Lev N. Sidorov ◽  
Shangfeng Yang ◽  
Tao Wei ◽  
...  
Keyword(s):  
Activation Barriers ◽  
Skeletal Transformation

How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? an Interlaboratory Study

2020 ◽  
Author(s):  
Saneyuki Ohno ◽  
Tim Bernges ◽  
Johannes Buchheim ◽  
Marc Duchardt ◽  
Anna-Katharina Hatz ◽  
...  
Keyword(s):  
Standard Deviation ◽  
Ionic Conductivity ◽  
Relative Standard Deviation ◽  
Solid Electrolytes ◽  
Ionic Conductivities ◽  
Ionic Conductors ◽  
Energy Storage Devices ◽  
Activation Barriers ◽  
Storage Devices ◽  
Relative Standard

<p>Owing to highly conductive solid ionic conductors, all-solid-state batteries attract significant attention as promising next-generation energy storage devices. A lot of research is invested in the search and optimization of solid electrolytes with higher ionic conductivity. However, a systematic study of an <i>interlaboratory reproducibility</i> of measured ionic conductivities and activation energies is missing, making the comparison of absolute values in literature challenging. In this study, we perform an uncertainty evaluation via a Round Robin approach using different Li-argyrodites exhibiting orders of magnitude different ionic conductivities as reference materials. Identical samples are distributed to different research laboratories and the conductivities and activation barriers are measured by impedance spectroscopy. The results show large ranges of up to 4.5 mScm<sup>-1</sup> in the measured total ionic conductivity (1.3 – 5.8 mScm<sup>-1</sup> for the highest conducting sample, relative standard deviation 35 – 50% across all samples) and up to 128 meV for the activation barriers (198 – 326 meV, relative standard deviation 5 – 15%, across all samples), presenting the necessity of a more rigorous methodology including further collaborations within the community and multiplicate measurements.</p>

Quasi-Barrierless Submolecular Motion in Mechanically Interlocked Carbon Nanotubes

2020 ◽  
Author(s):  
Julia Villalva ◽  
Belén Nieto-Ortega ◽  
Manuel Melle-Franco ◽  
Emilio Pérez
Keyword(s):  
Density Functional ◽  
Close Contact ◽  
Tight Binding ◽  
Energetic Cost ◽  
Molecular Fragments ◽  
Activation Barriers ◽  
Flat Surfaces ◽  
Different Types ◽  
Atomically Flat ◽  
Derivatives Of

The motion of molecular fragments in close contact with atomically flat surfaces is still not fully understood. Does a more favourable interaction imply a larger barrier towards motion even if there are no obvious minima? Here, we use mechanically interlocked rotaxane-type derivatives of SWNTs (MINTs) featuring four different types of macrocycles with significantly different affinities for the SWNT thread as models to study this problem. Using molecular dynamics, we find that there is no direct correlation between the interaction energy of the macrocycle with the SWNT and its ability to move along or around it. Density functional tight-binding calculations reveal small (<2.5 Kcal·mol-1) activation barriers, the height of which correlates with the commensurability of the aromatic moieties in the macrocycle with the SWNT. Our results show that macrocycles in MINTs rotate and translate freely around and along SWNTs at room temperature, with an energetic cost lower than the rotation around the C−C bond in ethane.<br>

Exploring the Influence of Substitution on the Structure and Transport Properties in the Sodium Superionic Conductor Na11+xSn2+x(Sb1−yPy)1−xS12

2020 ◽  
Author(s):  
Marvin Kraft ◽  
Lara Gronych ◽  
Theodosios Famprikis ◽  
Saneyuki Ohno ◽  
Wolfgang Zeier
Keyword(s):  
Electrochemical Impedance ◽  
Structural Phase ◽  
Ionic Transport ◽  
Sodium Ion ◽  
Ionic Conductors ◽  
Temperature Dependent ◽  
Activation Barriers ◽  
Rietveld Refinements ◽  
High Performing ◽  
The Given

<p>Sulfidic sodium ion conductors are currently investigated for the possible use in all-solid-state sodium ion batteries. The design of high performing electrolytes in terms of temperature-dependent ionic transport is based upon the fundamental understanding of structure – transport relationships within the given structural phase boundaries inherent to the investigated materials class. In this work, the Na<sup>+</sup> superionic structural family of Na<sub>11</sub>Sn<sub>2</sub>PS<sub>12</sub> is explored by using the systematic antimony substitution with phosphorous in Na<sub>11+<i>x</i></sub>Sn<sub>2+<i>x</i></sub>(Sb<sub>1-<i>y</i></sub>P<i><sub>y</sub></i>)<sub>1-<i>x</i></sub>S<sub>12</sub>. A combination of Rietveld refinements against X-ray synchrotron diffraction data with electrochemical impedance spectroscopy is used to monitor the changes in the anionic framework, the Na<sup>+</sup> substructure and the ionic transport. A new simplified descriptor for the average Na<sup>+</sup> diffusion pathways, the average Na<sup>+</sup> polyhedral volume is introduced, which is used to correlate the contraction of the overall lattice and the found activation barriers in the system. This study exemplifies how substitution affects diffusion pathways in ionic conductors and widens the knowledge about the related structural motifs and their influence on the ionic transport in this novel class of ionic conductors.</p>

Stereospecific 1,3-H Transfer of Indenols Proceeds via Persistent Ion-Pairs Anchored By NH···Pi Interactions

2018 ◽  
Author(s):  
David Ascough ◽  
Fernanda Duarte ◽  
Robert Paton
Keyword(s):  
Computational Analysis ◽  
Ion Pairs ◽  
Ion Pair ◽  
Hydrogen Atom Transfer ◽  
Polar Solvents ◽  
Chirality Transfer ◽  
Activation Barriers ◽  
Sense And Avoid ◽  
Phase Dynamics ◽  
Pi Interactions

The base-catalyzed rearrangement of arylindenols is a rare example of a suprafacial [1,3]-hydrogen atom transfer. The mechanism has been proposed to proceed via sequential [1,5]-sigmatropic shifts, which occur in a selective sense and avoid an achiral intermediate. A computational analysis using quantum chemistry casts serious doubt on these suggestions: these pathways have enormous activation barriers and in constrast to what is observed experimentally, they overwhelmingly favor a racemic product. Instead we propose that a suprafacial [1,3]-prototopic shift occurs in a two-step deprotonation/reprotonation sequence. This mechanism is favored by 15 kcal mol<sup>-1</sup> over that previously proposed. Most importantly, this is also consistent with stereospecificity since reprotonation occurs rapidly on the same p-face. We have used explicitly-solvated molecular dynamics studies to study the persistence and condensed-phase dynamics of the intermediate ion-pair formed in this reaction. Chirality transfer is the result of a particularly resilient contact ion-pair, held together by electrostatic attraction and a critical NH···p interaction which ensures that this species has an appreciable lifetime even in polar solvents such as DMSO and MeOH.

scholarly journals Anion ordering enables fast H− conduction at low temperatures

2021 ◽  
Vol 7 (23) ◽  
pp. eabf7883
Author(s):  
Hiroki Ubukata ◽  
Fumitaka Takeiri ◽  
Kazuki Shitara ◽  
Cédric Tassel ◽  
Takashi Saito ◽  
...  
Keyword(s):  
Ionic Conductivity ◽  
Room Temperature ◽  
Structural Transition ◽  
Hexagonal Lattice ◽  
Ionic Conductors ◽  
Activation Barriers ◽  
Energy Devices ◽  
Energy Applications ◽  
Chemical Disorder ◽  
New Energy

The introduction of chemical disorder by substitutional chemistry into ionic conductors is the most commonly used strategy to stabilize high-symmetric phases while maintaining ionic conductivity at lower temperatures. In recent years, hydride materials have received much attention owing to their potential for new energy applications, but there remains room for development in ionic conductivity below 300°C. Here, we show that layered anion-ordered Ba2−δH3−2δX (X = Cl, Br, and I) exhibit a remarkable conductivity, reaching 1 mS cm−1 at 200°C, with low activation barriers allowing H− conduction even at room temperature. In contrast to structurally related BaH2 (i.e., Ba2H4), the layered anion order in Ba2−δH3−2δX, along with Schottky defects, likely suppresses a structural transition, rather than the traditional chemical disorder, while retaining a highly symmetric hexagonal lattice. This discovery could open a new direction in electrochemical use of hydrogen in synthetic processes and energy devices.

Study of aerobic oxidation of phenyl PtII complexes (dpms)PtIIPh(L) (dpms = di(2-pyridyl)methanesulfonate; L = water, methanol, or aniline)

2009 ◽  
Vol 87 (1) ◽  
pp. 110-120 ◽  
Author(s):  
Julia R Khusnutdinova ◽  
Peter Y Zavalij ◽  
Andrei N Vedernikov
Keyword(s):  
Aqueous Solution ◽  
Aerobic Oxidation ◽  
Reductive Elimination ◽  
High Yield ◽  
Ambient Conditions ◽  
Activation Barriers ◽  
Methanol Solutions ◽  
Anionic Species ◽  
Mechanism Of Oxidation ◽  
Solution Mechanism

Oxidation of phenyl PtII complexes K[(dpms)PtIIPh2], 1, (dpms)PtIIPh(MeOH), 2, (dpms)PtIIPh(OH2), 3, and methyl PtII complex (dpms)PtIIMe(NH2Ph), 6, with O2 in aqueous or methanol solutions under ambient conditions leads to corresponding (dpms)PtIVR(X)OH complexes (R = X = Ph, 7; R = Ph, X = OH, 8; R = Ph, X = OMe, 9; R = Me, X = NHPh; 11; dpms = di(2-pyridyl)methanesulfonate). Complexes 7–9 could be isolated in high yield. Complex 11 as well as its phenyl analogue (dpms)PtIVPh(NHPh)OH, 10 can be prepared in high yield by oxidation of corresponding (dpms)PtIIR(NH2Ph) with H2O2 in methanol. Phenyl PtII complexes (dpms)PtIIPh(HX) derived from HX = aniline and DMSO, 4 and 5, respectively, are inert toward O2. The rate of oxidation of 1–5 with O2 decreases in the order 1 > 3 ~ 2 » 4, and 5 is unreactive. Methyl analogues are significantly more reactive compared with their phenyl counterparts. Proposed mechanism of oxidation with O2 includes formation of anionic species (dpms)PtIIR(X)– responsible for reaction with dioxygen. Attempts at C–O and C–N reductive elimination from phenyl PtIV complexes 7–10 do not lead to phenyl derivatives PhX at 80–100 °C, consistent with the results of the DFT estimates of corresponding activation barriers, ΔG0 exceeding 28 kcal/mol.Key words: platinum phenyl complexes, oxidation, dioxygen, aqueous solution, mechanism.

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