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11.
Magnus Pauly Julia Krger Viola Duppel Corban Murphey James Cahoon Bettina V. Lotsch Paul A. Maggard 《Chemical science》2022,13(11):3187
The in-depth understanding of the reported photoelectrochemical properties of the layered carbon nitride, poly(triazine imide)/LiCl (PTI/LiCl), has been limited by the apparent disorder of the Li/H atoms within its framework. To understand and resolve the current structural ambiguities, an optimized one-step flux synthesis (470 °C, 36 h, LiCl/KCl flux) was used to prepare PTI/LiCl and deuterated-PTI/LiCl in high purity. Its structure was characterized by a combination of neutron/X-ray diffraction and transmission electron microscopy. The range of possible Li/H atomic configurations was enumerated for the first time and, combined with total energy calculations, reveals a more complex energetic landscape than previously considered. Experimental data were fitted against all possible structural models, exhibiting the most consistency with a new orthorhombic model (Sp. Grp. Ama2) that also has the lowest total energy. In addition, a new Cu(i)-containing PTI (PTI/CuCl) was prepared with the more strongly scattering Cu(i) cations in place of Li, and most closely matching with the partially-disorder structure in Cmc21. Thus, a complex configurational landscape of PTI is revealed to consist of a number of ordered crystalline structures that are new potential synthetic targets, such as with the use of metal-exchange reactions.The layered carbon nitride, poly(triazine imide), exhibits a complex configurational landscape for the coordination of cations within its intralayer cavities that has been elucidated for the first time. 相似文献
12.
Concatenated coding provides a general strategy to achieve the desired level of noise protection in quantum information processing. We report the implementation of a concatenated quantum error-correcting code able to correct phase errors with a strong correlated component. The experiment was performed using liquid-state nuclear magnetic resonance techniques on a four spin subsystem of labeled crotonic acid. Our results show that concatenation between active and passive quantum error correction is a practical tool to handle realistic noise involving both independent and correlated errors. 相似文献
13.
The deprotonation of pentacarbonyl[(3-diethylamino-2,4-dimethyl)cyclobut-2-ene-1-ylidene]chromium (1d) and pentacarbonyl[(3-diethylamino-4-methyl-2-phenyl)cyclobut-2-ene-1-ylidene]chromium (1e) leads to antiaromatic conjugate anions by virtue of their being cyclobutadiene derivatives. Rate constants for the deprotonation of 1d and 1e by P2-Et and pKa values were determined in acetonitrile. Gas-phase B3LYP calculations of 1d, 1e, and their respective conjugate anions, using a generalized basis set, were also performed. Furthermore, for purposes of comparison with carbene complexes of similar structures, but having conjugate anions that are not antiaromatic, corresponding calculations were performed on pentacarbonyl[3-diethylamino-2,5-dimethyl)cyclopent-2-ene-1-ylidene]chromium (5), [dimethylamino(methyl)carbene]pentacarbonylchromium (3a), and [dimethylamino(iso-propyl)carbene]pentacarbonylchromium (3b) and their respective conjugate anions, and solution-phase pKa and kinetic measurements were carried out for 3a and 3b. Major points of interest include the effect of antiaromaticity on the kinetic and thermodynamic acidities of 1d and 1e, the large effect of the phenyl group on the gas-phase acidity of 1e, the strong attenuation of the acidities and the effect of the phenyl group in acetonitrile, and the position of the C=C double bonds in the cyclobutadiene ring of the conjugate anion of 1e. 相似文献
14.
Breakup densities of hot 197Au-like residues have been deduced from the systematic trends of Coulomb parameters required to fit intermediate-mass-fragment kinetic-energy spectra. The results indicate emission from nuclei near normal nuclear density below an excitation energy E(*)/A less, similar 2 MeV, followed by a gradual decrease to a near-constant value of rho/rho(0) approximately 0.3 for E(*)/A greater, similar 5 MeV. Temperatures derived from these data with a density-dependent Fermi-gas model yield a nuclear caloric curve that is generally consistent with those derived from isotope ratios. 相似文献
15.
MR-Relaxation (MRR) of 1H nuclei and MR-Cryoporometry (MRC) are combined to assess their feasibility and their potential in the study of bone microstructure. In principle, both techniques are able to give information on the structure of the pore space confining the fluids. Cow femur samples were carefully cored and cleaned in order to remove the natural fluids inside. For MRR analysis quasi-continuous distributions of T(1) and T(2) were obtained on samples fully saturated with water. Cyclohexane was used as a saturating fluid for MRC analysis. All T(1) and T(2) quasi-continuous distributions of water confined in bone samples are more than three decades wide, showing sufficient details to differentiate the samples. Pore size distributions obtained by MRC also differentiate the samples showing different characteristics of the pore space structure in the range of the highest sensitivity of the method (typically 3 to 100 nm, mesopore range). In particular, in samples where MRR shows a large fraction of signal with relaxation times below 10(2) ms, MRC indicates a large fraction of pore volume with pore sizes in the mesopore range. 相似文献
16.
17.
Katie Pei Dustin Banham Fangxia Feng Tobias Fürstenhaupt Siyu Ye Viola Birss 《Electrochemistry communications》2010,12(11):1666-1669
Two mesoporous carbons (with 15 (CIC-15) and 26 nm (CIC-26) diameter pores) were synthesized using a silica colloid imprinting method, loaded with 10 wt.% Pt, and then evaluated (against Vulcan? carbon (VC)) as oxygen reduction (ORR) catalysts for use in proton exchange membrane fuel cells. Both Pt/CICs reproducibly out-performed Pt/VC, with Pt/CIC-15 demonstrating higher ORR activity than Pt/CIC-26, despite its smaller pore size and lower surface area. Transmission electron tomography showed that the Pt nanoparticles (4–5 nm diameter) are fully deposited throughout the pores of the CICs and that the pore distribution in CIC-26 is partially ordered, while CIC-15 shows no ordering of its pores. Importantly, using the powerful imaging capabilities of transmission electron tomography, a first-time correlation is demonstrated between the ORR activity and the wall thickness of the carbon support materials. Pt/CIC-15 has significantly thicker walls, giving a lower measured electronic resistance, a lower ORR Tafel slope, and thus better performance overall compared to Pt/CIC-26. 相似文献
18.
A verification and validation procedure for yacht sail aerodynamics is presented. Guidelines and an example of application are provided. The grid uncertainty for the aerodynamic lift, drag and pressure distributions for the sails is computed. The pressures are validated against experimental measurements, showing that the validation procedure may allow the identification of modelling errors. Lift, drag and L2 norm of the pressures were computed with uncertainties of the order of 1%. Convergence uncertainty and round‐off uncertainty are several orders of magnitude smaller than the grid uncertainty. The uncertainty due to the dimension of the computational domain is computed for a flat plate at incidence and is found to be significant compared with the other uncertainties. Finally, it is shown how the probability that the ranking between different geometries is correct can be estimated knowing the uncertainty in the computation of the value used to rank. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
19.
An extension of the product operator formalism of NMR is introduced, which uses the Hadamard matrix product to describe many simple spin 1/2 relaxation processes. The utility of this formalism is illustrated by deriving NMR gradient-diffusion experiments to simulate several decoherence models of interest in quantum information processing, along with their Lindblad and Kraus representations. 相似文献
20.
In this paper the Mode-I elastodynamic problem of a crack propagating in an orthotropic medium is studied under the condition that the matrix of elastodynamic coefficients has repeated eigenvalues. It is shown that the crack is constrained in an elastodynamic state which is defined through a compulsory condition coupling its velocity with the elastic parameters of the orthotropic medium. The dynamic stress and displacement components ahead of the crack tip as well as the energy release rate are explicitly obtained. 相似文献