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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
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Dr. Dinar Abdullin Nico Fleck Christoph Klein Philipp Brehm Sebastian Spicher Prof. Dr. Arne Lützen Prof. Dr. Stefan Grimme Prof. Dr. Olav Schiemann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(10):2586-2596
Iron(III) porphyrins have the propensity to form μ2-oxo-dimers, the structures of which resemble two wheels on an axle. Whereas their crystal structure is known, their solution structure and internal dynamics is not. In the present work, the structure and dynamics of such dimers were studied by means of electron paramagnetic resonance (EPR) spectroscopy and quantum chemistry based molecular dynamics (MD) simulations by using the semiempirical tight-binding method (GFN-xTB). To enable EPR investigation of the dimers, a nitroxide was attached to each of the tetraphenylporphyrin cores through a linear and a bent linker. The inter-nitroxide distance distributions within the dimers were determined by continuous-wave (cw)-EPR and pulsed electron–electron double resonance (PELDOR or DEER) experiments and, with the help of MD, interpreted in terms of the rotation of the porphyrin planes with respect to each other around the Fe–O–Fe axis. It was found that such rotation is restricted to the four registers defined by the phenyl substituents. Within the registers, the rotation angle swings between 30° and 60° in the proximal and between 125° and 145° in the distal register. With EPR, all four angles were found to be equally populated, whereas the 30° and 145° angles are strongly favored to the expense of the 60° and 125° angles in the MD simulation. In either case, the internal dynamics of these dimers thus resemble the motion of a step motor. 相似文献
4.
Li-Miao Lin Yong-Hang Xu Man Shen Jia-Xin Liang Shuan-Jin Wang Min Xiao Yue-Zhong Meng 《高分子科学》2021,39(3):337-343
A series of semi-aromatic polyesters named as Poly(PO-CHO-PA) were facilely synthesized via ring-opening terpolymerization of biobased cyclohexane oxide(CHO)/propylene oxide(PO)/phthalic anhydride(PA) using economical U1/PPNCl as dual catalyst. The proportion of CHO-PA and PO-PA segments in polymer can be readily altered by changing the feed ratio of CHO/PO because the reactivity ratios of CHO and PO with PA calculated by Fineman-Ross method are comparable. All synthesized amorphous polyesters with various compositions show one Tg ranging from 62 ℃ to 133 ℃. Significantly, the mechanical, thermal and barrier properties of these amorphous semi-aromatic polyesters are also adjustable and investigated for the first time. The results indicate the semi-polyesters exhibit superior thermostability(T5% ranging from 306 ℃ to323 ℃) and high tensile strength(40.21-55.7 MPa) that is comparable with polystyrene(PS). Furthermore, Poly(PO-CHO-PA) films possess a promising prospect as packaging materials because of its colorless and highly transparent nature, along with low oxygen and water vapor transmission rate. All above performances may guarantee its potential alternative to commercial PS. 相似文献
5.
Giuseppe Spedalotto Dr. Robert Gericke Marta Lovisari Dr. Erik R. Farquhar Dr. Brendan Twamley Dr. Aidan R. McDonald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(51):11983-11990
Hydroxide-bridged high-valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis-μ-hydroxo-NiII2 complex ( 1 ) supported by a new dicarboxamidate ligand (N,N′-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two NiII ions and two bridging hydroxide ligands. Titration of the 1 e− oxidant (NH4)2[CeIV(NO3)6] with 1 at −45 °C showed the formation of the high-valent species 2 and 3 , containing NiIINiIII and NiIII2 diamond cores, respectively, maintaining the bis-μ-hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X-ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis-μ-hydroxide-NiIII2 3 was capable of oxidizing substrates at −45 °C at rates greater than that of the most reactive bis-μ-oxo-NiIII complexes reported to date. 相似文献
6.
This paper addresses the challenges of creating realistic models of soil for simulations of heavy vehicles on weak terrain. We modelled dense soils using the discrete element method with variable parameters for surface friction, normal cohesion, and rolling resistance. To find out what type of soils can be represented, we measured the internal friction and bulk cohesion of over 100 different virtual samples. To test the model, we simulated rut formation from a heavy vehicle with different loads and soil strengths. We conclude that the relevant space of dense frictional and frictional-cohesive soils can be represented and that the model is applicable for simulation of large deformations induced by heavy vehicles on weak terrain. 相似文献
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An efficient,mild and selective Ullmann‐type N‐arylation of indoles catalysed by Pd immobilized on amidoxime‐functionalized mesoporous SBA‐15 as heterogeneous and recyclable nanocatalyst 下载免费PDF全文
A wide range of N‐arylated indoles were selectively synthesized through intermolecular C(aryl)? N bond formation from the corresponding aryl iodides and indoles through Ullmann‐type coupling reactions in the presence of a catalytic amount of Pd immobilized on amidoxime‐functionalized mesoporous SBA‐15 (SBA‐15/AO/Pd(0)) under mild reaction conditions. These cross‐coupled products were obtained in excellent yields under mild conditions at extremely low palladium loading (ca 0.3 mol%), and the heterogeneous catalyst can be readily recovered by simple filtration and reused seven times with loss in its activity. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
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Ju‐You Lu Hong Wan Jianwei Zhang Zhixuan Wang Yang Li Yongmei Du Chunying Li Prof. Zhao‐Tie Liu Prof. Zhong‐Wen Liu Prof. Jian Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17542-17546
A palladium‐catalyzed direct C‐arylation reaction of readily available cage carboranyllithium reagents with aryl halides has been developed for the first time. This method is applicable to a wide range of aryl halide substrates including aryl iodides, aryl bromides, and heteroaromatic halides. 相似文献