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1.
Ab initio calculations have been performed to investigate some of the spectroscopic properties, like geometry, frequency, electron affinity, ionization potential and finally adiabatic bond dissociation energies (BDEs) of lead monohalides, lead dihalides and their ions viz. PbX, PbX±, PbX2, (X ?= ?F, Cl, Br, I) in their ground state at the QCISD(T)//MP2 level of theory using correlation consistent basis sets. For the validation of MP2 optimized geometry and frequency, we further obtained geometry and frequency of all the neutral and ionic systems using QCISD(T) method with the same basis sets. The BDEs of PbX2 molecules are calculated using the BDEs of ions and taking ionization potential and electron affinity of various systems. The calculated values are found in good agreement with the available data. Most of the data for ionic systems are reported first time in literature. 相似文献
2.
Samia Amara Joël Toulc'Hoat Laure Timperman Agnès Biller Hervé Galiano Corinne Marcel Matthieu Ledigabel Prof. Mérièm Anouti 《Chemphyschem》2019,20(4):581-594
The development of a suitable functional electrolyte is urgently required for fast-charging and high-voltage alkali-ion (Li, Na, K) batteries as well as next-generation hybrids supercapacitors. Many recent works focused on an optimal selection of electrolytes for alkali-ion based systems and their electrochemical performance but the understanding of the fundamental aspect that explains their different behaviour is rare. Herein, we report a comparative study of transport properties for LiPF6, NaPF6, KPF6 in acetonitrile (AN) and a binary mixture of ethylene carbonate (EC), dimethyl carbonate (DMC): (EC/DMC : 1/1, weigh) through conductivities, densities and viscosities measurements in wide temperature domain. By application of the Stokes-Einstein, Nernst-Einstein, and Jones Dole equations, the effective ionic solvated radius of cation (reff), the ionic dissociation coefficient (αD) and structuring Jones Dole's parameters (A, B) for salt are calculated and discussed according to solvent or cation nature as a function of temperature. From the results, we demonstrate that better mobility of potassium can be explained by the nature of the ion-ion and ion-solvent interactions due to its polarizability. In the same time, the predominance of triple ions in the case of K+, is a disadvantage at high concentration. 相似文献
3.
4.
The bond ionicity in seventy two ANB8−N compounds is investigated according to the recently introduced first-principles ionicity scale, based on the centers of the maximally localized Wannier functions, which has several interesting features. The obtained bond ionicities (qi) are found to exhibit the expected trends, according to electronegativity arguments. In particular, the bond ionicity in the alkaline-earth oxides increases by going from MgO to BaO. A strong crystal structure dependence of qi is observed. A critical value of qi (of 0.91) that separates between the tetrahedrally and octahedrally coordinated systems is inferred directly from the calculated values of qi. The volume dependence of qi is investigated for all the considered compounds and found to reduce by volume decrease for most of the studied systems. The adopted ionicity scale is established as a very strong competitor to the most widely accepted Phillips and Pauling ionicity measures. 相似文献
5.
Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq-13CO)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠ and ΔS≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF bond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation. 相似文献
6.
Dr. Ricardo Pérez de Tudela Prof. Dominik Marx 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(52):11955-11959
Acid dissociation, and thus liberation of excess protons in small water droplets, impacts on diverse fields such as interstellar, atmospheric or environmental chemistry. At cryogenic temperatures below 1 K, it is now well established that as few as four water molecules suffice to dissociate the generic strong acid HCl, yet temperature-driven recombination sets in simply upon heating that cluster. Here, the fundamental question is posed of how many more water molecules are required to stabilize a hydrated excess proton at room temperature. Ab initio path integral simulations disclose that not five, but six water molecules are needed at 300 K to allow for HCl dissociation independently from nuclear quantum effects. In order to provide the molecular underpinnings of these observations, the classical and quantum free energy profiles were decomposed along the dissociation coordinate in terms of the corresponding internal energy and entropy profiles. What decides in the end about acid dissociation, and thus ion pair formation, in a specific microsolvated water cluster at room temperature is found to be a fierce competition between classical configurational entropy and internal energy, where the former stabilizes the undissociated state whereas the latter favors dissociation. It is expected that these are generic findings with broad implications on acid–base chemistry depending on temperature in small water assemblies. 相似文献
7.
Domain-based local pair natural orbital methods within the correlation consistent composite approach
Ab initio composite approaches have been utilized to model and predict main group thermochemistry within 1 kcal mol−1, on average, from well-established reliable experiments, primarily for molecules with less than 30 atoms. For molecules of increasing size and complexity, such as biomolecular complexes, composite methodologies have been limited in their application. Therefore, the domain-based local pair natural orbital (DLPNO) methods have been implemented within the correlation consistent composite approach (ccCA) framework, namely DLPNO-ccCA, to reduce the computational cost (disk space, CPU (central processing unit) time, memory) and predict energetic properties such as enthalpies of formation, noncovalent interactions, and conformation energies for organic biomolecular complexes including one of the largest molecules examined via composite strategies, within 1 kcal mol−1, after calibration with 119 molecules and a set of linear alkanes. © 2019 Wiley Periodicals, Inc. 相似文献
8.
《Angewandte Chemie (International ed. in English)》2017,56(42):13041-13046
Studies with a series of metal/ceria(111) (metal=Co, Ni, Cu; ceria=CeO2) surfaces indicate that metal–oxide interactions can play a very important role for the activation of methane and its reforming with CO2 at relatively low temperatures (600–700 K). Among the systems examined, Co/CeO2(111) exhibits the best performance and Cu/CeO2(111) has negligible activity. Experiments using ambient pressure X‐ray photoelectron spectroscopy indicate that methane dissociates on Co/CeO2(111) at temperatures as low as 300 K—generating CHx and COx species on the catalyst surface. The results of density functional calculations show a reduction in the methane activation barrier from 1.07 eV on Co(0001) to 0.87 eV on Co2+/CeO2(111), and to only 0.05 eV on Co0/CeO2−x (111). At 700 K, under methane dry reforming conditions, CO2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. A significant part of the CHx formed on the Co0/CeO2−x (111) catalyst recombines to yield ethane or ethylene. 相似文献
9.
Dr. David F. León Rayo Ali Mansour Dr. Wenbin Wu Dr. Benjamin N. Bhawal Prof. Fabien Gagosz 《Angewandte Chemie (International ed. in English)》2023,62(3):e202212893
Direct C−H bond functionalization is a useful strategy for the straightforward formation of C−C and C−Heteroatom bonds. In the present work, a unique approach for the challenging electrophilic Au-catalyzed α-C−H bond functionalization of tertiary amines is presented. Electronic, steric and conformational synergistic effects exerted by the use of a malonate unit in the substrate were key to the success of this transformation. This new reactivity was applied to the synthesis of tetrahydro-γ-carboline products which, under oxidative conditions, could be converted into valuable structural motifs found in bioactive alkaloid natural products. 相似文献
10.
Shibing Zheng Dongjie Shi Tianjiang Sun Letian Zhang Weijia Zhang Yixin Li Zhenbo Guo Zhanliang Tao Jun Chen 《Angewandte Chemie (International ed. in English)》2023,62(9):e202217710
High-capacity small organic materials are plagued by their high solubility. Here we proposed constructing hydrogen bond networks (HBN) via intermolecular hydrogen bonds to suppress the solubility of active material. The illustrated 2, 7- diamino-4, 5, 9, 10-tetraone (PTO-NH2) molecule with intermolecular hydrogen (H) bond between O in −C=O and H in −NH2, which make PTO-NH2 presents transverse two-dimensional extension and longitudinal π–π stacking structure. In situ Fourier transform infrared spectroscopy (FTIR) has tracked the reversible evolution of H-bonds, further confirming the existence of HBN structure can stabilize the intermediate 2-electron reaction state. Therefore, PTO-NH2 with HBN structure has higher active site utilization (95 %), better cycle stability and rate performance. This study uncovers the H-bond effect and evolution during the electrochemical process and provides a strategy for materials design. 相似文献