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41.
42.
We use molecular simulation to probe the connection between local structure and the unusual re-entrant dynamics observed for polydisperse hard-sphere liquids confined in thin slit pores. The local structure is characterised by calculating 2-D bond-orientational order parameters associated with square and hexatic order for particles in the layer adjacent to the confining walls. When the wall separation is commensurate with the average particle size, the particles primarily exhibit local hexatic order, whereas local square order increases in prevalence for incommensurate geometries. The relaxation time extracted from the ensemble-averaged mean-square displacement increases exponentially with the static correlation length associated with hexatic local order in strongly confined commensurate geometries, in agreement with theoretical predictions for dynamical slowing. Square order, by contrast, is not associated with a growing length scale for either commensurate or incommensurate geometries, indicating that it is strongly geometrically frustrated. Our results suggest that the influence of bond-orientational order on dynamical slowing may be altered by changing the extent of confinement. 相似文献
43.
We study the nature of the smectic–isotropic phase transition using a mobile 6-state Potts model. Each Potts state represents a molecular orientation. We show that with the choice of an appropriate microscopic Hamiltonian describing the interaction between individual molecules modeled by a mobile 6-state Potts spins, we observe the smectic phase dynamically formed when we cool the molecules from the isotropic phase to low temperatures (T). In order to elucidate the order of the transition and the low-T properties, we use the high-performance Wang–Landau flat energy-histogram technique. We show that the smectic phase goes to the liquid (isotropic) phase by melting/evaporating layer by layer starting from the film surface with increasing T. At a higher T, the whole remaining layers become orientationally disordered. The melting of each layer is characterized by a peak of the specific heat. Such a succession of partial transitions cannot be seen by the Metropolis algorithm. The successive layer meltings/evaporations at low T are found to have a first-order character by examining the energy histogram. These results are in agreement with experiments performed on some smectic liquid crystals. 相似文献
44.
The task of reconstructing the system’s state from the measurements results, known as the Pauli problem, usually requires repetition of two successive steps. Preparation in an initial state to be determined is followed by an accurate measurement of one of the several chosen operators in order to provide the necessary “Pauli data”. We consider a similar yet more general problem of recovering Feynman’s transition (path) amplitudes from the results of at least three consecutive measurements. The three-step histories of a pre- and post-selected quantum system are subjected to a type of interference not available to their two-step counterparts. We show that this interference can be exploited, and if the intermediate measurement is “fuzzy”, the path amplitudes can be successfully recovered. The simplest case of a two-level system is analysed in detail. The “weak measurement” limit and the usefulness of the path amplitudes are also discussed. 相似文献
45.
ABSTRACTThis study computes the potential energy curves of the X1Σ+, A1Π, B1Δ, C1Σ+, and D1Π states of AlO+ cation and the transition dipole moments between them. The orders of the rotationless radiative lifetimes are 10–100?μs for the A1Π state, 1–1000?ms for the B1Δ state, 10?ns for the first well and 100?ns for the second well of the C1Σ+ state, and 1?μs for the D1Π state. Emissions of the B1Δ–A1Π and D1Π–C1Σ+ systems are so weak that they are hardly measured via spectroscopy, the emissions of the C1Σ+–X1Σ+, C1Σ+–A1Π, and D1Π–X1Σ+ systems are so strong that they can be detected readily, and emissions of the A1Π–X1Σ+ and D1Π–A1Π systems can be observed through spectroscopy only by a significant effort. There is a strong great similarity between spontaneous emissions of the A1Π–X1Σ+ system of the AlO+ cation and the A2Π–X2Σ+ system of the AlO radical. The emissions of the A2Π–X2Σ+ system of the AlO radical have been measured in outer space Therefore, it is highly possible that the emissions of the A1Π–X1Σ+ system of the AlO+ cation can be detected in the astrophysical media. 相似文献
46.
Dr. Haixiang Han Jesse C. Carozza Audra P. Colliton Yuxuan Zhang Dr. Zheng Wei Dr. Alexander S. Filatov Prof. Dr. Yu-Sheng Chen Melisa Alkan Prof. Dr. Andrey Yu. Rogachev Prof. Dr. Evgeny V. Dikarev 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(24):9711-9717
A known trinuclear structure was used to design the heterobimetallic mixed-valent, mixed-ligand molecule [CoII(hfac)3−Na−CoIII(acac)3] ( 1 ). This was used as a template structure to develop heterotrimetallic molecules [CoII(hfac)3−Na−FeIII(acac)3] ( 2 ) and [NiII(hfac)3−Na−CoIII(acac)3] ( 3 ) via isovalent site-specific substitution at either of the cobalt positions. Diffraction methods, synchrotron resonant diffraction, and multiple-wavelength anomalous diffraction were applied beyond simple structural investigation to provide an unambiguous assignment of the positions and oxidation states for the periodic table neighbors in the heterometallic assemblies. Molecules of 2 and 3 are true heterotrimetallic rather than a statistical mixture of two heterobimetallic counterparts. Trinuclear platform 1 exhibits flexibility in accommodating a variety of di- and trivalent metals, which can be further utilized in the design of molecular precursors for the NaMM′O4 functional oxide materials. 相似文献
47.
Pengjin Qin Li-An Wang Prof. Joseph M. O'Connor Prof. Kim K. Baldridge Yifan Li Burak Tufekci Jiyue Chen Prof. Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18114-18121
Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C5H5)Ru(NCMe)3]PF6 as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations. 相似文献
48.
The electronic (energy gap and work function) as well as electrical properties (dipole moment, polarizability, and first hyperpolarizabilities) of the first-row transition metals decorated C24N24 cavernous nitride fullerene were explored using DFT calculations. The transition metals are decorated at N4 cavity of C24N24 fullerene. According to our spin polarized computations, the most stable spin state monotonically increases to sextet for Mn@C24N24 and thereafter dropped off gradually to singlet state for Zn@C24N24 system. The findings demonstrate that transition metals can remarkably decrease the HOMO-LUMO energy gap and work function values up to 63% and 21% of bare C24N24, respectively. As can be seen, when the Sc and Ti metals are located above the N4 cavity of fullerene, systems of enhanced static hyperpolarizabilities (β0) are delivered. These findings might provide an effective strategy to design high performance eletcro-optical materials based on carbon- nitride fullerene. 相似文献
49.
A structurally stable, 3d-4f heterometallic coordination polymer has been solvothermally synthesised and evaluated for its accomplished materials properties. The light absorption activity in the visible band was higher for unique Ce-Fe MOF than that of the homometallic Ce-MOF or Fe- MOF. The intimate overlap of two different metal clusters in heterometallic environmental induced the formation of low line conduction orbital, which ultimately lowered the transition energy. The heterometallic acquired an additional sensitisation from a Fe-μ3-oxo cluster that had vibrantly enhanced the light uptake activity. The vacancy created in the 6s, 5d orbital of Ce in Ce-Fe MOF contributed to the photo-excitation of electrons and reduced the recombination time. This distinct intramolecular arrangement assisted the exciton trapping characteristic. Also, the presence of multiple metal cores in the framework aided to confine the increased number of excitons for a redox reaction. The solar photocatalysis study with acetaminophen revealed these improved materialistic features by degrading it 94.6% with a rate constant of 0.0137 min−1. The recycle studies confirmed the robust stability of the synthesised MOF. 相似文献
50.
Lifen Wang Lei Liu Ji Chen Ali Mohsin Jung Hwan Yum Todd W. Hudnall Christopher W. Bielawski Tijana Rajh Xuedong Bai Shang-Peng Gao Gong Gu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(36):15864-15870
Using high-resolution transmission electron microscopy and electron energy-loss spectroscopy, we show that beryllium oxide crystallizes in the planar hexagonal structure in a graphene liquid cell by a wet-chemistry approach. These liquid cells can feature van-der-Waals pressures up to 1 GPa, producing a miniaturized high-pressure container for the crystallization in solution. The thickness of as-received crystals is beyond the thermodynamic ultra-thin limit above which the wurtzite phase is energetically more favorable according to the theoretical prediction. The crystallization of the planar phase is ascribed to the near-free-standing condition afforded by the graphene surface. Our calculations show that the energy barrier of the phase transition is responsible for the observed thickness beyond the previously predicted limit. These findings open a new door for exploring aqueous-solution approaches of more metal-oxide semiconductors with exotic phase structures and properties in graphene-encapsulated confined cells. 相似文献