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The paper presents an algorithm for calculating the three-dimensional Voronoi–Delaunay tessellation for an ensemble of spheres of different radii (additively-weighted Voronoi diagram). Data structure and output of the algorithm is oriented toward the exploration of the voids between the spheres. The main geometric construct that we develop is the Voronoi S-network (the network of vertices and edges of the Voronoi regions determined in relation to the surfaces of the spheres). General scheme of the algorithm and the key points of its realization are discussed. The principle of the algorithm is that for each determined site of the network we find its neighbor sites. Thus, starting from a known site of the network, we sequentially find the whole network. The starting site of the network is easily determined based on certain considerations. Geometric properties of ensembles of spheres of different radii are discussed, the conditions of applicability and limitations of the algorithm are indicated. The algorithm is capable of working with a wide variety of physical models, which may be represented as sets of spheres, including computer models of complex molecular systems. Emphasis was placed on the issue of increasing the efficiency of algorithm to work with large models (tens of thousands of atoms). It was demonstrated that the experimental CPU time increases linearly with the number of atoms in the system, O(n). © 2006 Wiley Periodicals, Inc. J Comput Chem, 2006 [ABSTRACT FROM AUTHOR]

Rate coefficients for alkyl and alkoxy radical decomposition are important in combustion, biological, and atmospheric processes. In this paper, rate constant expressions for C1&bond;C4 alkyl and alkoxy radicals decomposition via β-scission are recommended based on the reverse, exothermic reaction, the addition of a hydrogen atom or an alkyl radical to an olefin or carbonyl species with the decomposition reaction calculated using microscopic reversibility. The rate expressions have been estimated based on a wide-range study of available experimental data. Rate coefficients for hydrogen atom and alkyl radical addition to an olefin show a strong temperature curvature. In addition, it is found that there is a correlation between the activation energy for addition and (i) the type of atom undergoing addition and (ii) whether this radical adds to the internal or terminal carbon atom of the olefin. Rate coefficients for alkoxy radical decomposition show a strong correlation to the ionization potential of the alkyl radical leaving group and on the enthalpy of reaction. It is shown that the activation energy for alkyl radical addition to a carbonyl species can be estimated as a function of the alkyl radical ionization potential and enthalpy of reaction. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 250–275, 2006 [ABSTRACT FROM AUTHOR]

Precise calculations of core properties in heavy-atom systems that are described by the operators heavily concentrated in atomic cores, such as hyperfine structure and P,T-parity nonconservation effects, require accounting for relativistic effects. Unfortunately, four-component calculation of molecules containing heavy elements is very consuming already at the stages of calculation and transformation of two-electron integrals with a basis set of four-component spinors. In turn, the relativistic effective core potential (RECP) calculations of valence (spectroscopic, chemical, etc.) properties of molecules are very popular, because the RECP method allows one to treat quite satisfactorily the correlation and relativistic effects for the valence electrons of a molecule and to reduce significantly the computational efforts. The valence molecular spinors are usually smoothed in atomic cores, and, as a result, direct calculation of electronic densities near heavy nuclei is impossible. In this paper, the methods of nonvariational and variational one-center restoration of correct shapes of four-component spinors in atomic cores after a two-component RECP calculation of a molecule are discussed. Their efficiency is illustrated in correlation calculations of hyperfine structure and parity nonconservation effects in heavy-atom molecules YbF, BaF, TlF, and PbO. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [ABSTRACT FROM AUTHOR]

X-ray geometries of monocycloalkenobenzenes with a fused- ring size of r = 5, 6 were obtained by the use of the Cambridge Structural Database. In contrast to Allen's study [Acta Cryst. (1981), B37, 900–906], the data were not averaged over exact or imposed mad symmetry (mad is the mirror plane going through the midpoint of the aromatic ring fusion bond and the aromatic bond parallel to it). The distribution of the non- aromatic endocyclic angle ε at the ring fusion clearly shows two and three, respectively, distinct curves for r = 5 and r = 6. The respective ranges are 104.3–112.6 and 104.4-123.2°. If one of the C atoms directly attached to the aromatic ring is sp2 hybridized, the bond length e between the aromatic ring and this atom is shortened by some 0.044 (15) and 0.027 (12) Å for r = 5 and r = 6, respectively. However, for r = 5, e is only shortened by 0.030 (17) Å when both C atoms directly attached to the aromatic ring are sp2 hybridized. For r = 5, the endocyclic angle ε is 1.2 (13)° smaller at the side involving the sp2 hybridized C atom. [ABSTRACT FROM AUTHOR]

Direct methods have been applied to the SIR (single isomorphous replacement) case to estimate structure-factor moduli from diffraction magnitudes. The joint probability distribution function P(EH, Ep, E,d) has been calculated by explicitly considering, as an additional primitive random variable, the cumulative error arising from measurements and from lack of isomorphism. The specific feature of the approach is that it provides estimated values of EH which depend on the experimental diffraction data as well as on errors. Some test structures have been used to check the efficiency of the new estimates. Patterson techniques, using the estimated EH² values as coefficients, as well as a tangent procedure, have been implemented into a computer program to locate the heavy atoms automatically. All the experimental tests show that the new approach provides results highly competitive with the traditional EH² estimates. [ABSTRACT FROM AUTHOR]

The differences between two databases describing the polypeptide main chain in terms of charge-density parameters, directly usable in protein structure refinements, are discussed. These databases contain averaged multipole populations of peptide pseudo-atoms obtained from refinement against theoretical simulated data and against high-resolution experimental data on small peptide or amino acid molecules. The main discrepancy becomes apparent when electrostatic properties are calculated. [ABSTRACT FROM AUTHOR]

Probabilistic direct-methods phasing theory, origin ally based on a uniform atomic distribution hypothesis, is shown to be adaptable to a non-uniform bulk-solvent-compensated globbic approximation for protein crystals at low resolution. The effective number ng of non-H protein atoms per polyatomic glob increases with decreasing resolution; low-resolution phases depend on the positions of only Ng = Na/Ng globs rather than Na atoms. Test calculations were performed with measured structure-factor data and the refined structural parameters from a protein crystal with ∼ 10 000 non-H protein atoms per molecule and ∼ 60% solvent volume. Low-resolution data sets with dmin ranging from 15 to 5 Å gave ng = admin + b, with a = 1.0 Å-1 and b = -1.9 for the test case. Results of tangent- formula phase-estimation trials emphasize that completeness of the low-resolution data is critically important for probabilistic phasing. [ABSTRACT FROM AUTHOR]

This paper shows that the bulk wave that is radiated to the inside of the substrate in the excitation and propagation of a leaky surface acoustic wave (LSAW) can be suppressed by forming a proton-exchanged layer on the surface of the substrate. It is theoretically shown that, even if the electrical condition of the propagation path is a free surface, the particle displacement distribution of the LSAW particle is concentrated at the substrate surface by proton exchange, as in the case of a metallized surface. This result suggests that the bulk wave radiation in LSAW excitation can be suppressed. The bulk wave radiation loss is examined by measuring the insertion loss between the input and the output IDT on the 41° Y-X LiNbO3 substrate, and it is shown that the bulk wave can be reduced to zero by proton exchange. It is shown experimentally that the leak loss in the propagation due to the bulk wave radiation can be reduced to approximately one-third by the proton exchange. © 1999 Scripta Technica, Electron Comm Jpn Pt 3, 83(1): 44–52, 2000 [ABSTRACT FROM AUTHOR]

Elucidating single‐atom effects on the fundamental properties of nanoparticles is challenging because single‐atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu58H20PET36(PPh3)4]2+ (Cu58; PET: phenylethanethiolate; PPh3: triphenylphosphine) nanocluster—an atomically precise nanoparticle—that can be transformed into the surface‐defective analog [Cu57H20PET36(PPh3)4]+ (Cu57). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu57. Remarkably, the loss of this single surface atom drastically alters the reactivity of the nanocluster. In contrast to Cu58, Cu57 shows promising activity for click chemistry, particularly photoinduced [3+2] azide‐alkyne cycloaddition (AAC), which is attributed to the active catalytic site in Cu57 after the removal of one surface copper atom. Our study not only presents a unique system for uncovering the effect of a single‐surface atom modification on nanoparticle properties but also showcases single‐atom surface modification as a powerful means for designing nanoparticle catalysts. [ABSTRACT FROM AUTHOR]

Photoexcitation of trapped ions by Hermite–Gaussian (HG) modes from guided beam structures is proposed and investigated theoretically. In particular, simple analytical expressions for the matrix elements of induced atomic transitions are derived that depend both on the parameters of HG beams and on the geometry of an experiment. By using these general expressions, the 2S1/2→2F7/2$^{2}S_{1/2} \rightarrow \; ^{2}F_{7/2}$ electric octupole (E3) transition is investigated in an Yb+ ion, localized in the low–intensity center of the HG10 and HG01 beams. It is shown how the corresponding Rabi frequency can be enhanced by properly choosing the polarization of incident light and the orientation of an external magnetic field, which defines the quantization axis of a target ion. The calculations, performed for experimentally feasible beam parameters, indicate that the achieved Rabi frequencies can be comparable or even higher than those observed for the conventional Laguerre–Gaussian (LG) modes. Since HG‐like modes can be relatively straightforwardly generated with high purity and stability from integrated photonics, these results suggest that they may form a novel tool for investigating highly‐forbidden atomic transitions. [ABSTRACT FROM AUTHOR]

Open‐[60]fullerenes possessing a huge orifice with a ring‐atom count exceeding 19 have been confined to only a few examples. Herein, we report a 20‐membered‐ring orifice which enables for a guest molecule such as H2, N2, and CH3OH to be encapsulated inside the [60]fullerene cavity. In addition, a 21‐membered‐ring orifice was prepared via a reductive decarbonylation, in which one of the carbon atoms was moved out of the [60]fullerene skeleton as an N,N‐dimethylamide group. At a low temperature of −30 °C, an Ar atom was encapsulated with an occupation level up to 52 %. At around room temperature, the amide group on the orifice rotates along with the C(amide)−C(fullerene) bond axis, realizing a self‐inclusion of the methyl substituent on the amide group as confirmed NMR spectroscopically and computationally. [ABSTRACT FROM AUTHOR]

An atroposelective Ir‐catalyzed dynamic kinetic resolution (DKR) of 2‐(quinolin‐8‐yl)benzaldehydes/1‐naphthaldehydes by transfer hydrogenative coupling of allyl acetate is disclosed. The allylation reaction takes place with simultaneous installation of central and axial chirality, reaching high diastereoselectivities and excellent enantiomeric excesses when ortho‐cyclometalated iridium‐DM‐BINAP is used as the catalyst. The racemization of the substrates occurs through a designed transient Lewis acid‐base interaction between the quinoline nitrogen atom and the aldehyde carbonyl group. [ABSTRACT FROM AUTHOR]

The asymmetric hydrophosphination of cyclopropenes with phosphines is of much interest and importance, but has remained hardly explored to date probably because of the lack of suitable catalysts. We report here the diastereo‐ and enantioselective hydrophosphination of 3,3‐disubstituted cyclopropenes with phosphines by a chiral lanthanocene catalyst bearing the C2‐symmetric 5,6‐dioxy‐4,7‐trans‐dialkyl‐substituted tetrahydroindenyl ligands. This protocol offers a selective and efficient route for the synthesis of a new family of chiral phosphinocyclopropane derivatives, featuring 100 % atom efficiency, good diastereo‐ and enantioselectivity, broad substrate scope, and no need for a directing group. [ABSTRACT FROM AUTHOR]

Cascade aza‐Piancatelli reaction and [3+3]/[4+2] cycloaddition reactions are carried out using the ideality principles of pot, atom, and step economy (PASE) synthesis. The reaction resulted in generation of octahydro‐4H‐cyclopenta[b]pyridin‐6‐one scaffolds. Moreover, octahydro‐5,7a‐epoxycyclopenta[cd]isoindol‐4‐one frameworks of gracilamine alkaloid and a novel decahydro‐1H‐dicyclopenta[cd,hi]isoindol‐6‐one were also realized in good yields with excellent regio‐ and diastereo‐selectivities. [ABSTRACT FROM AUTHOR]

The first case of successful suppression of the coordination of a lithium atom with a dialkylamino group by the effective conjugation of the latter with the aromatic core has been discovered. This effect controls regioselectivity of the bromine−lithium exchange in 4,6,7,9‐tetrabromo‐1,3‐dimethyl‐2,3‐dihydro‐1H‐perimidine, which leads to products with the most effective conjugation. As a result, the product of this quadruple exchange demonstrates no tendency of the coordination of the NMe groups to neighboring lithium atoms despite the absence of steric restrictions. Experimental results are explained by means of quantum chemical calculations: geometry optimization, natural bond analysis and scans using the modredundant scheme. [ABSTRACT FROM AUTHOR]

Triboraazabutenyne 3 is synthesized by the reaction of diboraazabutenyne 1 with aryl boron dibromide followed by the reduction. The ligand exchange to replace phosphine on the terminal sp2 B atom with carbene furnishes 4. 11B NMR, solid‐state structures, and computational studies disclose that 3 and 4 feature the extremely polarized B=B bond. 4 readily splits the N=N bond of both diazo compound and diazirine under ambient conditions, whereby one nitrogen atom is incorporated into the B=B moiety leading to a neutral diboraazaallene 6. The mechanism of the reaction between 4 and diazo compound is extensively investigated by density functional theory (DFT) calculations, as well as the isolation of an intermediate. [ABSTRACT FROM AUTHOR]

A number of two‐deck dicationic 3a,6a‐diaza‐1,4‐diphosphapentalenes (DDP)2X2 (X=halogen or complex ion) have been characterized. Interdeck distances P(1)⋅⋅⋅P(3) and P(2)⋅⋅⋅P(4) in crystal structures, as a rule, significantly exceed the sum of covalent radii, however they are still within the sum of van der Waals radii. The 31P NMR data indicate that phosphorus atoms are equivalent in solution even at low temperatures (233 K). Based on DFT calculations, the formation of two equivalent P−P covalent bonds (<2.4 Å) is energetically unfavorable, despite the absence of steric barriers. The total energy of the model dication as a function of the P⋅⋅⋅P separation has a minimum at the P−P distance of 2.85 Å. This distance corresponds to the highest aromaticity index in the interdeck space (NICS(1.0)=−20.72). The energy of interdeck interactions is estimated at 10–15 kcal/mol. [ABSTRACT FROM AUTHOR]

Chelotropic reactions are widely used in organic synthesis. These reactions are of the pericyclic type where a π bond and a lone pair are transformed into a pair of sigma bonds; with both sigma bonds added to the same atom. This work presents an analysis of several representative chelotropic reactions. To study the reaction path, we have divided it into two parts, from the reactants to the transition state and from the transition state to the products which has allowed us to compare the behavior of the reactants in these two ranges of the path. To perform the analysis, global reactivity descriptors based on the conceptual‐density functional theory (DFT), such as electrophilicity and global softness, have been calculated. To analyze these descriptors, the corresponding local descriptors have been used. A model based on Sanderson's principle (electronegativity equalization principle), developed previously, has been used to calculate the local reactivity descriptors (atomic). The statistical methodology of multiple regression analysis has been used to determine which local variables are the most relevant for the global parameter under study (softness, and electrophilicity), also the principal component analysis has been used as a guide to estimate the number of variables to take into account in the analysis, finally this has led us to important correlations between global and local parameters which has allowed us to analyze the reactions of the study. Transition states of the reactions are aromatic as obtained from the nucleus independent chemical shift (NICS) and gauge including magnetically induced ring current (GIMIC) analysis. [ABSTRACT FROM AUTHOR]

NGDY has high‐N atom doping rate, many active sites, large pore size, outstanding thermal stability, and excellent lithium‐ion storage properties. The mixed adsorption of the Mn‐modified NGDY (Mn‐NGDY) system has been studied with the first principles approach, which shows the effects and the mechanism of action about the modified Mn atom and H2 molecules on the adsorption of CH4. From the results, more electrons are transferred from the Mn atom to the neighboring six‐membered ring, making the Mn atom positively charged and forming a strong Coulomb interaction with the substrate. There is Coulomb interaction between the first two methane molecules and Mn atoms, and CH4 molecules have strong polarization phenomenon under this interaction, which causes the surrounding CH4 molecules of the first layer (The CH4 molecules around the first two CH4 molecules) inducing polarization along the XY plane (parallel substrate), and the surrounding CH4 molecules of the second layer inducing polarization along the Z‐axis direction, which improve the adsorption properties of other CH4 molecules. In the first layer, the interaction forces of the adsorbed CH4 molecules region mainly come from the interaction forces between CH4 and the substrate, and the interaction forces between CH4 molecules dominate in the adsorption of second layer. Polarization of H2 molecules along the Z‐axis direction causes the formation of a weak negative center above it, which promotes the adsorption of CH4 molecules above it. For the 2Mn‐NGDY system, a maximum of 72 CH4 molecules and 4 H2 molecules can be adsorbed simultaneously on both sides, when the average adsorption energy and adsorption amount reach −0.169 eV and 73.41 wt%. [ABSTRACT FROM AUTHOR]

Four new diorganotin(IV) complexes, including Me2SnL(1), Bu2SnL(2), Ph2SnL(3) and Oct2SnL(4), were synthesized by reacting R2SnCl2 (where R = Me, Bu, Ph, Oct) with N′‐(3,5‐dichloro‐2‐hydroxybenzylidene)‐2‐phenylacetohydrazide H2L. The synthesized ligand and complexes were structurally characterized by various techniques, including Fourier transform infrared (FT‐IR), 1H and 13C nuclear magnetic resonance (NMR) and mass spectrometry. The data suggested that tin–oxygen and tin–nitrogen bonds are formed during complex formation, confirming the coordination of ligand with dialkyltin(IV) moieties and the presence of penta‐coordinated structures. The single‐crystal X‐ray study was performed to confirm the molecular structure of complex 1, which revealed that the molecular structure is distorted towards square pyramidal geometry. The compound–DNA interaction was investigated via spectroscopic, electrochemical and molecular docking studies; the mode of interaction found in all cases was intercalative in nature. The complex 3 showed the highest binding ability with sodium salt of salmon sperm DNA (SS‐DNA) (1.93 × 105 M−1). The data obtained for DNA interaction studies from theoretical calculation via docking studies match well with those observed from spectroscopic and electrochemical analyses. Electrochemical and thermodynamic parameters, including diffusion coefficient, ∆H, ∆G and ∆S, were also calculated. The DPPH antioxidant results showed that complex 2 is an active antioxidant. [ABSTRACT FROM AUTHOR]

Non‐carbon‐supported single‐atom electrocatalysts (SACs) have attracted tremendous research interest for water splitting, owning to their remarkable differences in bond and coordination, and better and tunable catalytic performance, compared with those carbon‐supported SACs and commercial catalysts. The electrocatalytic performance of these non‐carbon‐supported SACs is intimately related to the structure, surficial chemical groups, and vacancy defects of non‐carbon host materials, as well as the physico‐chemical properties and population of single atoms. The much widened range of host materials and types of single atoms create virtually limitless opportunities in the design of SACs with tunable structures and electrocatalysis behaviors. In this review, the recent progress of non‐carbon‐supported SACs for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is visited, where the unique local structures, electrocatalytic performance, catalytic centers and key preparation processes are presented. The characterizations down to atomic scales that can reveal the key local structures and catalytic mechanism are also investigated. New insights into the correlations between the structural evolution of these SACs during electrocatalytic reactions and their catalytic performance are examined. Finally, the major challenges faced by these new SACs are summarized, together with future perspectives on the rational design of superior non‐carbon‐supported SACs. [ABSTRACT FROM AUTHOR]

Inspired by the d‐band center theory, previous studies mainly focus on transition metals as electrocatalytic active sites. The s‐block metals in the periodic table, especially group ΙA metals with fewer valence electrons, are rarely reported as high‐activity electrocatalysts for reduction reactions due to the difficulties associated with their electronic structure regulation. Herein, theoretical calculations demonstrate that group ΙA element lithium (Li) embedded in N, O‐doped graphene is an effective electrocatalytic active center for carbon dioxide reduction reaction (CO2RR) and oxygen reduction reaction (ORR). This catalytic feasibility results from the s–p orbital hybridization between originally empty 2p orbital of Li and the orbitals of coordinated atoms. This vacant 2p orbital can serve as a site for additional p–π conjugation between Li and N, O‐doped graphene. Theoretically, the zigzag‐type Li–O2 model shows remarkable CO2RR activity, while Li–pyridinic–N1‐C1 exhibits high ORR activity. Furthermore, a carbon‐based catalyst with well‐anchored Li atoms coordinated to N, O substituents is experimentally demonstrated to exhibit exceptional CO2RR activity (FECO = 98.8% at −0.55 V) and ORR performance in acidic media (E1/2 = 0.77 V). This is the first report on bifunctional high‐performance electrocatalyst utilizing a group ΙA element with performance comparable to that of most previously reported transition‐metal‐based catalysts. [ABSTRACT FROM AUTHOR]

The employing visible light to drive organic transformations is the most promising choice to meet the needs for green synthesis, in which the reactions promoted by visible light may provide a more efficient and greener method. Currently, the most abundant methods for activation and functionalization of reaction substrates have relied on the direct single‐electron transfer (SET) between the excited photocatalyst and substrates, and these wonderful works were summarized and docoumented in many reviews. As a complement to the above reactions, the photoredox‐mediated atom transfer transformations (photocatalyst‐to‐HAT catalyst‐to‐substrates) to generate radical species are showing an explosively growing trend. In this review, we highlight recent significant developments in this rapidly growing area, mainly focusing on the photoinduced base‐to‐substrates charge transfer reactions. [ABSTRACT FROM AUTHOR]

Organic electrode materials based on conjugated dicarboxylate moieties are particularly attractive to develop metal‐ion organic batteries. Exhibiting good stability properties in liquid electrolytes, such organic electrode materials can reversibly store alkali metal ions (Li, Na or K) at low working potential. Although many molecular designs have been investigated in the last decade, conjugated dicarboxylates are impeded by low coulombic efficiencies, especially at the first cycle, and sluggish kinetics in most cases. Herein, a new strategy in the design of conjugated carboxylates by fusing a thiadiazole heterocycle to the terephthalate core is reported. The synthesis and electrochemical performance of dilithium‐2,1,3‐benzothiadiazole‐4,7‐dicarboxylate (Li2‐DCBTZ) as positive electrode material is investigated for the first time. Next to being a new structural design, the presence of the thiadiazole ring enables (i) a better conjugation of π‐n electrons leading to a benefit in terms of rate capability, and (ii) a better stabilizing coordination network for Li ions through both oxygen and nitrogen atoms. In addition, the reduced state in Li4‐DCBTZ is stabilized due to a maintained aromaticity in the heteroaromatic core in comparison to the parent terephthalate. Theoretical calculations on the Li‐ion storage mechanism and bonding character support the experimental work. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A new electrochemical strategy for the atom transfer radical addition (ATRA) of polychloroalkanes across olefins has been realized by the synergism of paired electrolysis and halogen bonding activation. Notably, readily accessible 4,4‐di‐tert‐butyl bipyridine (dtbpy), acting as a halogen bonding acceptor, shifted the reduction potential of C—Cl bonds positively by 110 mV. The decreased operating potential leads to a wide substrate scope and excellent functional group compatibility. A diverse array of terminal and internal alkenes such as (hetero)aryl olefins, unactive aliphatic olefins, and natural products and drugs‐derived olefins were well compatible. [ABSTRACT FROM AUTHOR]

In this work, a coupled system of two V‐type atoms with dipole–dipole interaction in a dissipative single‐mode cavity, which couples with an external environment, is studied. The analytical solution of this model is obtained by solving the time dependent Schrodinger equation after Hamiltonian of dissipative cavity is diagonalized by introducing a set of new creation and annihilation operators according to Fano theorem. It is also discussed in detail how the entanglement dynamics of different initial states are influenced by the cavity‐environment coupling, the spontaneously generated interference (SGI) parameter, and the dipole–dipole interaction between two atoms. The results show that the SGI parameter has different effects on entanglement dynamics under different initial states. Namely, the SGI parameter will increase the decay rate of the initially maximal entangled state and reduce that of the initially partial entangled state. For the initially product state, the larger SGI parameter corresponds to the more entanglement generated. The entanglement monotonically decreases under the weak cavity‐environment coupling, while the oscillation of entanglement will occur under the strong cavity‐environment coupling. The larger the dipole–dipole interaction is, the slower the entanglement decays and the more the entanglement will be generated. So the dipole–dipole interaction can not only protect and generate entanglement very effectively, but also enhance the regulation effect of the SGI parameter on entanglement. [ABSTRACT FROM AUTHOR]

Breaking the time‐reversal symmetry of light is of great importance for fundamental physics and has attracted increasing interest in the study of non‐reciprocal photonic devices. Here, a chiral cavity quantum electrodynamics system with multiple atoms strongly coupled to a Fabry–Pérot cavity is experimentally demonstrated. By polarizing the internal quantum state of the atoms, the time‐reversal symmetry of the atom‐cavity interaction is broken. The strongly coupled atom‐cavity system can be described by non‐reciprocal quasiparticles, that is, the cavity polariton. When it works in the linear regime, the inherent nonreciprocity makes the system work as a single‐photon‐level optical isolator. Benefiting from the collective enhancement of multiple atoms, an isolation ratio exceeding 30 dB on the single‐quanta level (≈ 0.1 photon on average) is achieved. The validity of the non‐reciprocal device under zero magnetic field and the reconfigurability of the isolation direction are also experimentally demonstrated. Moreover, when the cavity polariton works in the nonlinear regime, the quantum interference between polaritons with weak anharmonicity induces non‐reciprocal nonclassical statistics of cavity transmission from coherent probe light. [ABSTRACT FROM AUTHOR]

The symmetry-mode analysis of a structural phase transition involves the use of methods of the representation theory of space groups. The aim of the paper is to present an alternative approach for the determination of the primary and secondary symmetry modes that contribute to the structural distortion of the low-symmetry, phase. It only requires the systematic use of the data from International Tables for Crystallography, Vol. A. and is based on a fact. well known to crystallographers: the fully symmetrical displacements of any orbit of atoms (i.e. the modes compatible with the symmetry of the structure) follow in a straightforward way from the coordinate triplets of the corresponding Wyckoff positions. This property, systematically used for all intermediate subgroups between the space groups of the two phases, allows the determination of the relevant symmetry modes. Their distraction into primary, and secondary modes comes out directly in the process of calculation. As an example, primary and secondary modes m the ferroelectric distortion of potassium selenate are divided. [ABSTRACT FROM AUTHOR]

The high-field currents in poly-p-chloroxylylene (PCPX) thin films are due to hole injection from anode metal and collision ionization. PPX thin films showed the negative temperature dependence of high-field currents. Since the chlorine atoms in PCPX thin films act as carrier scattering centers, high-Field currents in PCPX thin films are suppressed in the low-temperature region. This paper discusses the high-field currents of PCPX/PPX composite thin films; these films are PCPX thin films (d < 150 nm) deposited on PPX thin films (d < 200 nm). They were strongly suppressed at room temperature, but not at low temperature. Therefore, PCPX/PPX composite thin films showed a remarkable negative temperature dependence of high-field currents. High-field currents were suppressed more in PCPX (60 nm)/PPX (230 nm) composite thin film than in PCPX (130 nm)/ PPX (230 nm). This can he explained by the suppression of the hole injection from anode by homo space charge at the interface between PCPX/PPX. [ABSTRACT FROM AUTHOR]

The phosphorothioate analog of ATP has a sulfur atom replacing a non-bridging oxygen atom of the triphosphate moiety of ATP. Due to the tetrahedral nature of the phosphorus atom, stereoisomers are known to exist, designated as the Sp and Rp isomers. We have reported [Shimizu & Furusawa (1986) Biochemistry 25, 5787] on the hydrolytic activity of the 22S dynein from Tetrahymema cilia towards the phosphorothioate analogs of ATP. In this paper, we extend our study and report on the microtubule-dynein dissociation by these analogs and on their ability to support sea urchin flagellar dynein enzymatic activity as well as ciliary or flagellar motility. It has been shown that the microtubules — 22s-dyein complex is dissociated by the binding of ATP to the enzymatic sites [Porter & Johnson (1983) J. Biol. Chem. 258, 6575]. We studied the dissociation by adenosine 5’-[α-thio]triphosphate (ATP[αS]), Sp and Rp, by light-scattering stopped-flow methods. The dissociation by (Sp)ATP[αS] was rapid and the rate of the light-scattering change by (Sp)ATP[αS] was a hyperbolic function of the nucleotide concentration, indicating that dissociation was a two-step process. On the other hand, (Rp )ATP[αS] up to 2 mM induced only slow and partial dissociation of the complex, while, in the presence of vanadate, it induced complete dissociation with a slightly higher rate (0.5 s-1). The adenosine 5’-[β-thio]triphosphate (ATP[βS]) isomers did not induce dissociation. The hydrolytic activity of the outer arm dyein from sea urchin sperm flagella towards these analogs was similar to that of 22S dynein. The ratios of Vmax (nmol · mg protein-1 · min-1)/apparent Km (µM) of this dynein were 400-720, 53, 9.7, 0.62 and 0.028 for ATP, ATP[αS] (Sp or Rp), ATP[βS] (Sp or Rp), respectively, in the presence of Mg2+ as the supporting cation. This dynein exhibited the same stereospecificity at β phosphate as the 22S dynein or myosin. The detergent models of Tetrahymena or sea urchin spermatozoa were reactivated only by ATP or (Sp)ATP[αS] while other analogs were ineffective. The maximal beat frequency of the cilia or flagella reactivated by (Sp)ATP[αS] was one‐quarter to one‐half of that produced by ATP reactivation. [ABSTRACT FROM AUTHOR]

The Fourier transform NMR (nuclear magnetic resonance) spectroscopy is used widely at present as a noninvasive method in the structural analysis of macromolecules in organic chemistry and in the metabolic study of tissue and cells in biochemistry. We believe, however, that the Fourier transform is not adequate in the determination of the density distribution of the nucleus. The NMR signal contains essentially the relaxation (a kind of damping) phenomena, but the Fourier transform does not take this fact into consideration. Consequently, the obtained NNR spectrum is degraded both in intensity and resolution, providing apparent nucleus density distribution which is different from the true value. This paper proposes an estimation of the NNR spectrum, which positively takes the relaxation phenomenon into consideration. The method is derived by extending the Kalman filter to the complex stochastic system and applying the result to the NMR signal represented by the complex stochastic system. The proposed method is applied to the NMR signal of proton (114) obtained from mayonnaise in 2[T] static magnetic field. The result is compared with the NMR spectrum obtained by the Fourier transform, and it is shown that the resolution and the intensity are improved drastically. [ABSTRACT FROM AUTHOR]

A representation of polymer self‐consistent field theory equivalent to quantum density functional theory is given in terms of non‐orthogonal basis sets. Molecular integrals and self‐consistent equations for spherically symmetric systems using Gaussian basis functions are given, and the binding energies and radial electron densities of neutral atoms hydrogen through krypton are calculated. An exact electron self‐interaction correction is adopted and the Pauli‐exclusion principle is enforced through ideas of polymer excluded‐volume. The atoms hydrogen through neon are examined without some approximations which permit cancellation of errors and spontaneous shell structure is observed. Correlations are neglected in the interest of simplicity and comparisons are made with Hartree–Fock theory. The implications of the Pauli‐exclusion potential and its approximate form are discussed, and the Pauli model is analyzed using scaling theory for the uniform electron density case where the correct form of the Thomas–Fermi quantum kinetic energy and the Dirac exchange correction are recovered. [ABSTRACT FROM AUTHOR]

Allenes (>C=C=C<) are classified as cumulated dienes with a linear structure and an sp‐hybridized central carbon atom. We have synthesized and isolated a stable 2‐germapropadiene with bulky silyl substituents. The 2‐germapropadiene allene moiety adopts a linear structure both in the solid state and in solution. An X‐ray diffraction electron‐density‐distribution (EDD) analysis of this 2‐germapropadiene confirmed the linear C=Ge=C geometry with a formally sp‐hybridized germanium atom that bears two orthogonal C=Ge π‐bonds. Based on detailed structural and computational studies, we concluded that the linear geometry of the isolated 2‐germapropadiene most likely arises from the negative hyperconjugation of the silyl substituents at the terminal carbon atoms. The 2‐germapropadiene reacts rapidly with nucleophiles, indicating that the linearly oriented germanium atom is highly electrophilic. [ABSTRACT FROM AUTHOR]

Herein, the diffusion and distribution of hydrogen (H) atoms in ferrite and bainite contained in an X80 pipeline steel is studied by both scanning Kelvin probe force microscopy and finite‐element modeling. The effect of metallurgical microphases on H‐atom accumulation in the steel is analyzed. The results show that H‐charging elevates the electrochemical dissolution activity of both ferrite and bainite contained in the steel, as indicated by the increased Volta potential and thus the decreased work function. The H atoms tend to accumulate at ferrite, making the local H‐atom concentration much greater than the concentration at bainite. The results imply that, compared with bainite, ferrite is the location to accumulate more H atoms initiating hydrogen‐induced cracks once the local H‐atom concentration reaches a threshold value. [ABSTRACT FROM AUTHOR]

Single‐atom catalysts (SACs) are a popular area of research for clean energy conversion owing to their cost‐effectiveness and excellent performance. The support plays a vital role in uniformly stabilizing and dispersing the single atoms. Although easily accessible carbon (C) is commonly selected as a support for SACs, its electrochemical properties, particularly stability, usually limits its application. Recently, non‐C materials with flexible physicochemical properties and unique metal–support interactions have attracted increasing attention for loading isolated metal atoms, showing promise for promoting catalytic performance. Therefore, in this review, a comprehensive summary of current research developments in non‐C‐supported SACs for green energy conversion is provided. The review begins with a brief introduction of the four types of non‐C‐supported SACs based on the support used. Thereafter, a systemic summary of synthesis methods for non‐C‐supported SACs analyzing their advantages and disadvantages is provided. The interactions between single metal atoms and non‐C supports are discussed, followed by their applications in green energy conversion. Then, the significance of adopting a variety of in situ/operando approaches is emphasized to gain insight into both the synthesis and reaction mechanisms, which have been successfully deployed for non‐C‐supported SACs. Finally, the remaining challenges and perspectives on designing promising non‐C‐supported SACs are discussed. [ABSTRACT FROM AUTHOR]

Synthesis, bonding and chemistry of mono‐ and bimetallic complexes supported by chelating thiolato ligands have been established. Treatment of [Cp*VCl2]3 (1) with [LiBH4 ⋅ THF] followed by the addition of ethane‐1,2‐dithiol led to the formation of an EPR active bimetallic vanadium thiolato complex [(Cp*V){μ‐(SCH2CH2S)‐κ2S,S′)2{V(SCH2CH2S‐SH)}] (2). In complex 2, two ethane‐1,2‐dithiolato ligands are symmetrically coordinated to two vanadium atoms through μ‐S atoms. Interestingly, when similar reactions were carried out with heavier group 5 metal precursors, such as [Cp*NbCl4] (3 a), it afforded monometallic thiolato complex [Cp*Nb(SCH2CH2S)(SCH2CH2S−CH2S)] (4 a). On the other hand, the Ta‐analogue [Cp*TaCl4] (3 b) yielded thiolato species [Cp*Ta(SCH2CH2S)(SCH2CH2S−CH2S)] (4 b) and [Cp*Ta(SCH2CH2S) (SCH2CH2S−S)] (5). In complexes 4 a and 4 b, one ethane‐1,2‐dithiolato and one trithiolato ligand are coordinated to Nb and Ta centers, respectively. Whereas, in complex 5, one ethane‐1,2‐dithiolato and one 2‐disulfanylethanethiolato is coordinated to the Ta center. Moreover, the photolytic reaction of 5 with [Mo(CO)5 ⋅ THF] yielded heterobimetallic thiolato complex [(Cp*Ta){μ‐(SCH2CH2S)‐κ2S,S′}{μ‐(SCH2CH2S−CH2(CH3)S)κ2S′′ : κ1S‐′′′′ : κ1S′′′′′}{Mo(CO)3}] (6). All the complexes have been characterized by multinuclear NMR spectroscopy and single crystal X‐ray diffraction studies. Further, computational analyses were performed to provide an insight into the bonding of these complexes. [ABSTRACT FROM AUTHOR]

Herein, we synthesized pnictogen (P, As, Sb)‐ and chalcogen (O, S)‐containing diheteroanthracene derivatives with 8π‐electron systems. As opposed to the pnictogen atoms, the chalcogen atoms significantly affected the conformations of the diheteroanthracenes. In addition, the S‐containing compounds exhibited relatively large Stokes shifts owing to significant structural relaxations compared with those of the O‐containing compounds. Computational calculations revealed that the bent conformations of the S‐containing compounds in their ground states planarized upon photoexcitation. [ABSTRACT FROM AUTHOR]

Two well‐defined novel binuclear cobalt (II) [Co(H2L1)]2 and [Co(H2L2)]2 compounds are presented. Binuclear cobalt (II) complexes (1–2) containing 1,1′‐binaphthyl derived tetradentate (N2O2) donor ligands H2L1 and H2L2, namely 3,3‐bis[((2,6‐diisopropylphenyl)imino)methyl]‐[1,1′‐binaphthalene‐2,2′‐dioxodicobalt(II) and 3,3′‐bis‐[((2,6‐diethyl‐phenyl)imino)‐ethyl]‐[1,1′]‐binaphtyl‐2,2′‐dioxocobalt(II) complexes were synthesized and isolated for the first time. Various spectroscopic techniques, including UV‐visible spectra, magnetic susceptibility, cyclic voltammetry, elemental analysis, mass spectrometry, and single‐crystal X‐ray diffraction were used to structurally characterize these binuclear cobalt(II) complexes. The binuclear cobalt (II) [Co(H2L1)]2 and [Co(H2L2)]2 complexes (1–2) demonstrated excellent catalytic activity in the cyanosilylation reaction of various aryl aldehydes to value‐added cyanohydrins at room temperature under solvent‐free conditions. [ABSTRACT FROM AUTHOR]

Accurate estimation of solvation free energy (SFE) lays the foundation for accurate prediction of binding free energy. The Poisson‐Boltzmann (PB) or generalized Born (GB) combined with surface area (SA) continuum solvation method (PBSA and GBSA) have been widely used in SFE calculations because they can achieve good balance between accuracy and efficiency. However, the accuracy of these methods can be affected by several factors such as the charge models, polar and nonpolar SFE calculation methods and the atom radii used in the calculation. In this work, the performance of the ABCG2 (AM1‐BCC‐GAFF2) charge model as well as other two charge models, that is, RESP (Restrained Electrostatic Potential) and AM1‐BCC (Austin Model 1‐bond charge corrections), on the SFE prediction of 544 small molecules in water by PBSA/GBSA was evaluated. In order to improve the performance of the PBSA prediction based on the ABCG2 charge, we further explored the influence of atom radii on the prediction accuracy and yielded a set of atom radius parameters for more accurate SFE prediction using PBSA based on the ABCG2/GAFF2 by reproducing the thermodynamic integration (TI) calculation results. The PB radius parameters of carbon, oxygen, sulfur, phosphorus, chloride, bromide and iodine, were adjusted. New atom types, on, oi, hn1, hn2, hn3, were introduced to further improve the fitting performance. Then, we tuned the parameters in the nonpolar SFE model using the experimental SFE data and the PB calculation results. By adopting the new radius parameters and new nonpolar SFE model, the root mean square error (RMSE) of the SFE calculation for the 544 molecules decreased from 2.38 to 1.05 kcal/mol. Finally, the new radius parameters were applied in the prediction of protein‐ligand binding free energies using the MM‐PBSA method. For the eight systems tested, we could observe higher correlation between the experiment data and calculation results and smaller prediction errors for the absolute binding free energies, demonstrating that our new radius parameters can improve the free energy calculation using the MM‐PBSA method. [ABSTRACT FROM AUTHOR]

The design of a well‐ordered arrangement of atoms on a solid surface has long been sought due to the envisioned applications in many different fields. On‐surface synthesis of metal‐organic networks is one of the most promising fabrication techniques. Hierarchical growth, which involves coordinative schemes with weaker interactions, favours the formation of extended areas with the desired complex structure. However, the control of such hierarchical growth is in its infancy, particularly for lanthanide‐based architectures. Here the hierarchical growth of a Dy‐based supramolecular nanoarchitecture on Au(111) is described. Such an assembly is based on a first hierarchical level of metallo‐supramolecular motifs, which in a second level of hierarchy self‐assemble through directional hydrogen bonds, giving rise to a periodic two‐dimensional supramolecular porous network. Notably, the size of the metal‐organic based tecton of the first level of hierarchy can be tailored by modifying the metal‐ligand stoichiometric ratio. [ABSTRACT FROM AUTHOR]

[Mn3O(OAc)7(HOAc)]6 ⋅ x AcOH (x=6–9) represents a rare example of a compound containing molecular Mn18‐rings. These are formed by Mn3(μ3‐O) subunits in which the high‐spin Mn(III) centers are bridged by three pairs of acetate anions (AcO−). An AcOH molecule coordinates to one of the Mn atoms leading to [Mn3(μ3‐O)(μ2‐OAc)6(AcOH)]‐units, designated in short as Mn3‐units, that are interconnected by acetate anions via the other two Mn atoms to form Mn18‐rings. Magnetic measurements show weak ferromagnetic interactions between them that are suppressed in strong magnetic field. Quantum‐chemical calculations on Mn3 model complexes using independently DFT and ab‐initio multi reference methods (CASSCF/NEVPT2) show a correlation between the orientation of the pseudo‐Jahn‐Teller axes of pairs of Mn(III) magnetic centers and corresponding exchange coupling energies. Weak coupling between Mn3‐units within the Mn18‐ring allowed to simulate the magnetic susceptibility versus temperature dependence in terms of basically uncoupled magnetic moments of each Mn3‐unit within the ring. [ABSTRACT FROM AUTHOR]

Single atoms and nanoclusters of Fe, Ni, Co, Cu, and Mn are systematically designed and embedded in a well‐defined C1N1‐type material that has internal cavities of ≈0.6 nm based on four N atoms. These N atoms serve as perfect anchoring points for the nucleation of small nanoclusters of different metal natures through the creation of metal‐nitrogen (TM‐N4) bonds. After pyrolysis at 800 °C, TM@CNx‐type structures are obtained, where TM is the transition metal and x < 1. Fe@CNx and Co@CNx are the most promising for oxygen reduction reaction and hydrogen evolution reaction, respectively, with a Pt‐like performance, and Ni@CNx is the most active for oxygen evolution reaction (OER) with an EOER of 1.59 V versus RHE, far outperforming the commercial IrO2 (EOER = 1.72 V). This systematic and benchmarking study can serve as a basis for the future design of advanced multi‐functional electrocatalysts by modulating and combining the metallic nature of nanoclusters and single atoms. [ABSTRACT FROM AUTHOR]

In decades, heterogeneous catalysis has played a more significant role in social progress. However, the exorbitant price and low reserves vastly limit the application of noble metal catalysts, which are extensively used in heterogeneous catalysis. The single‐atom‐alloy catalysts (SAAs) have been regarded as a crucial way to improve the dispersion ratio of noble metal while maintaining great heterogeneous catalytic performance by dispersing noble metal single atoms on the surface of another metal. Besides the benefit from the metal bonds between noble metals and support metals, SAAs is also a unique method to construct metallic metal single atoms and obtain its characteristic catalytic performance, which is not possessed by other single atoms catalysts with positive electricity metal atoms. Most recently, SAAs have been demonstrated to catalyze a lot of significant heterogeneous reactions. This review will introduce the synthesis methods of SAAs and then summarize their applications in heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

Despite extensive efforts to develop high‐performance H2 evolution catalysts, this remains a major challenge. Here, we demonstrate the use of Cd/Pt precursor solutions for significant photocatalytic H2 production (154.7 mmol g−1 h−1), removing the need for a pre‐synthesized photocatalyst. In addition, we also report simultaneous in situ synthesis of Pt single‐atoms anchored CdS nanoparticles (PtSA‐CdSIS) during photoirradiation. The highly dispersed in situ incorporation of extensive Pt single atoms on CdSIS enables the enhancement of active sites and suppresses charge recombination, which results in exceptionally high solar‐to‐hydrogen conversion efficiency of ≈1 % and an apparent quantum yield of over 91 % (365 nm) for H2 production. Our work not only provides a promising strategy for maximising H2 production efficiency but also provides a green process for H2 production and the synthesis of highly photoactive PtSA‐CdSIS nanoparticles. [ABSTRACT FROM AUTHOR]

We revisit the generalized pseudospectral (GPS) method to investigate the physical properties of shell‐confined atoms. Based on a general mapping function, the GPS method is developed for obtaining highly accurate bound state energies, wave functions, and radial quantities for the shell‐confined hydrogen atom. Besides the incidental and simultaneous degeneracies in the energy spectrum, we find that energy degeneracy appears very commonly in the shell‐confined system. The contour maps of the eigenenergies for some low‐lying bound states are obtained and the corresponding wave functions are analyzed. Radial expectation values with both positive and negative powers are calculated with high accuracy. By analyzing the Schwarz‐like inequalities, we show that the ground state density function for the outer‐confined hydrogen atom is second‐order monotonic, while for the shell‐confined hydrogen atom the radial densities for all bound states are zeroth‐order monotonic. In the extreme situation when the inner radius coalesces with the outer radius, the electron becomes a classical particle. [ABSTRACT FROM AUTHOR]

The first 1,4‐distibabenzene‐1,4‐diide compound [(ADC)Sb]2 (5) based on an anionic dicarbene (ADC) (ADC=PhC{N(Dipp)C}2, Dipp=2,6‐iPr2C6H3) is reported as a bordeaux‐red solid. Compound 5, featuring a central six‐membered C4Sb2 ring with formally SbI atoms may be regarded as a base‐stabilized cyclic bis‐stibinidene in which each of the Sb atoms bears two lone‐pairs of electrons. 5 undergoes 2 e‐oxidation with Ph3C[B(C6F5)4] to afford [(ADC)Sb]2[B(C6F5)4]2 (6) as a brick‐red solid. Each of the Sb atoms of 6 has an unpaired electron and a lone‐pair. The broken‐symmetry open‐shell singlet diradical solution for (6)2+ is calculated to be 2.13 kcal mol−1 more stable than the closed‐shell singlet. The diradical character of (6)2+ according to SS‐CASSCF (state‐specific complete active space self‐consistent field) and UHF (unrestricted Hartree‐Fock) methods amounts to 36 % and 39 %, respectively. Treatments of 6 with (PhE)2 yield [(ADC)Sb(EPh)]2[B(C6F5)4]2 (7‐E) (E=S or Se). Reaction of 5 with (cod)Mo(CO)4 affords [(ADC)Sb]2Mo(CO)4 (8). [ABSTRACT FROM AUTHOR]

Mechanically interlocked molecules (MIMs) have gained increasing interest during the last decades, not only because of their aesthetic appeal, but also because their unique properties have allowed them to find applications in nanotechnology, catalysis, chemosensing and biomedicine. Herein we describe how a pyrene molecule with four octynyl substituents can be easily encapsulated within the cavity of a tetragold(I) rectangle‐like metallobox, by template formation of the metallo‐assembly in the presence of the guest. The resulting assembly behaves as a mechanically interlocked molecule (MIM), in which the four long limbs of the guest protrude from the entrances of the metallobox, thus locking the guest inside the cavity of the metallobox. The new assembly resembles a metallo‐suit[4]ane, given the number of protruding long limbs and the presence of the metal atoms in the host molecule. However, unlike normal MIMs, this molecule can release the tetra‐substituted pyrene guest by the addition of coronene, which can smoothly replace the guest in the cavity of the metallobox. Combined experimental and computational studies allowed the role of the coronene molecule in facilitating the release of the tetrasubstituted pyrene guest to be explained, through a process that we named "shoehorning", as the coronene compresses the flexible limbs of the guest so that it can reduce its size to slide in and out the metallobox. [ABSTRACT FROM AUTHOR]

Thermolysis of a 1 : 1 mixture of tris(di‐tert‐butylmethylsilyl)germane 9 and bis(di‐tert‐butylmethylsilyl)germane 17 at 100 °C produces unexpectedly octagermacubane 18, having two 3‐coordinate Ge0 atoms (40 % yield). 18 was characterized by X‐ray crystallography and it is a singlet biradical (according to DFT quantum mechanical calculations and the absence of an EPR signal). Reactions of 18 with CH2Cl2 and H2O yield the novel dichloro‐octagermacubane 24 and hydroxy‐octagermacubane 25, respectively. Reduction of 18 with tBuMe2SiNa in THF produces an isolable octagermacubane radical anion 26‐Na. Based on X‐ray crystallography, EPR spectroscopy and DFT quantum mechanical calculations, 26‐Na is classified as a Ge‐centered radical anion. [ABSTRACT FROM AUTHOR]

Perovskite materials are widely used in the fields of luminescence and light energy conversion with the advantages of low cost and outstanding optoelectronic properties. However, abundant surface lattice defects heavily affect the performances of perovskite optoelectronic devices. Here, by treating surface defects with oleylamine molecules in situ, the surface trap states are significantly decreased in a CsPbBr3 microplate, enabling photoluminescence intensity and carrier lifetimes to be dramatically enhanced and prolonged, respectively. These interesting phenomena can be attributed to the binding of undercoordinated Pb atoms with N atoms on the surface of perovskite microplate. The strong binding energy of lead‐halogen bonds inhibits the photodegraded reactions of the crystal, leading to the significant improvement of luminescent stability for the microplate correspondingly. The results not only provide experimental guidance for passivating lattice defects but also pave the way for improving the efficiency of wide materials and optoelectronic devices. [ABSTRACT FROM AUTHOR]