Why do dipole moments of HCl-water clusters fail to determine acid dissociation?

This paper quantitatively examines why dipole moments of HCl(H2O)n=1-8 cannot serve as the dissociation criterion for acid molecules using the Hirshfeld-I approach. Also, we propose the possible experimental parameter 〈P(HCl)〉, whose statistical average enables the assessment of acid dissociation in mixed clusters. Furthermore, our calculations reveal that a minimum of four water molecules are necessary to dissociate an HCl molecule.

Enhanced magnetic anisotropy of iridium dimers on antisite defects of two-dimensional transition-metal dichalcogenides.

The combination of transition-metal (TM) elements with two-dimensional (2D) transition-metal dichalcogenides (TMDs) provides an effective route to realizing a 2D controllable magnetic order, leading to significant applications in multifunctional nanospintronics. However, in most TM atoms@TMDs nanostructures, it is challenging for the magnetic anisotropy energy (MAE) to exceed 30 meV when affected by the crystal field. Hence, the stronger magnetic anisotropy of TMDs has yet to be developed. Here, utilizing first-principle calculations based on density functional theory (DFT), a feasible method to enhance the MAEs of TMDs via configurating iridium dimers (Ir2) on 2D traditional and Janus TMDs with antisite defects is reported. Calculations revealed that 28 of the 54 configurations considered possessed structure-dependent MAEs of >60 meV per Ir2 in the out-of-plane direction, suggesting the potential for applications at room temperature. We also showed the ability to tune the MAE further massively by applying a biaxial strain as well as the surface asymmetric polarization reversal of Janus-type substrates. This approach led to changes to >80 meV per Ir2. This work provides a novel strategy to achieve tunable large magnetic anisotropy in 2D TMDs. It also extends the functionality of antisite-defective TMDs, thereby providing theoretical support for the development of magnetic nanodevices.

Electrically controlled nonvolatile switching of single-atom magnetism in a Dy@C84 single-molecule transistor.

Single-atom magnetism switching is a key technique towards the ultimate data storage density of computer hard disks and has been conceptually realized by leveraging the spin bistability of a magnetic atom under a scanning tunnelling microscope. However, it has rarely been applied to solid-state transistors, an advancement that would be highly desirable for enabling various applications. Here, we demonstrate realization of the electrically controlled Zeeman effect in Dy@C84 single-molecule transistors, thus revealing a transition in the magnetic moment from 3.8 µ B to 5.1 µ B for the ground-state GN at an electric field strength of 3 - 10 MV/cm. The consequent magnetoresistance significantly increases from 600% to 1100% at the resonant tunneling point. Density functional theory calculations further corroborate our realization of nonvolatile switching of single-atom magnetism, and the switching stability emanates from an energy barrier of 92 meV for atomic relaxation. These results highlight the potential of using endohedral metallofullerenes for high-temperature, high-stability, high-speed, and compact single-atom magnetic data storage.

Flexible MA2Z4 (M = Mo, W; A = Si, Ge and Z = N, P, As) monolayers with outstanding mechanical, dynamical, electronic, and piezoelectric properties and anomalous dynamic polarization.

We systematically investigate the mechanical, dynamical, and piezoelectric properties of MA2Z4 monolayers (M = Mo, W; A = Si, Ge and Z = N, P, As) based on first-principles calculations. The structural properties, cohesive energy and formation energy analyses show that all of the considered MA2Z4 monolayers are dynamically stable. Ab initio molecular dynamics simulations further indicate that the MA2Z4 monolayers can sustain stability at high temperatures. The MA2Z4 monolayers exhibit isotropic mechanical properties with the bearable largest strains exceeding 25% and 30% in the armchair and zigzag directions. All MA2Z4 monolayers exhibit semiconducting properties, and the band gaps change in a wide range. The piezoelectric constants e11 and d11 increase from 3.21 × 10-10 to 8.17 × 10-10 C m-1 and 0.73 to 6.05 pm V-1, respectively. We reveal that the piezoelectric coefficients are closely related to the ratio of the polarizabilities of the isolated anions and cations. Infrared spectroscopy indicates that the piezoelectricity is the overlap of the intrinsic dipole moments existing in the inner MZ2 monolayer and outer A2Z2 bilayer. Besides, the Born effective charges quantificationally show the contribution of component atoms to polarization. The anomalous dynamic polarization around M atoms is found, which is generated from the anti-bonding of the last occupied orbital. Our results indicate that the MA2Z4 monolayers have great potential in piezotronics and piezo-phototronics fields.

Correlation and Prognostic Assessment of Low T3 Syndrome and Norepinephrine Dosage for Patients with Sepsis: A Retrospective Single-Center (Cohort) Study.

Purpose: To investigate the correlation and prognostic significance of low triiodothyronine (T3) syndrome and norepinephrine dosage in patients with sepsis and septic shock. Methods: This single-center, retrospective, cohort study enrolled 169 patients with sepsis and septic shock that were admitted to the intensive care unit of First Hospital of Nanchang, Nanchang, China from June 2017 to July 2019. All included patients were followed up for 28 days or died, whichever was earlier. Patients with free T3 (FT3) of <3.1 pmol/L were considered with low T3 syndrome. The correlation and prognostic significance of the FT3 and maximum dosage of norepinephrine (MDN) within 72 h, as well as other clinical indicators, were analyzed by using correlation analysis, principal component analysis, receiver operating characteristic curve, Youden index, and logistic regression. Results: A total of 138 patients were allocated to the low T3 group. FT3 inversely correlated with the Sequential Organ Failure Assessment (SOFA) score within 24 h, fluid resuscitation volume within 24 h, and lactic acid levels, and positively correlated with the mean arterial pressure. The critical values of age, SOFA, and MDN for predicting the 28-day mortality were 79.5 years, 8.5 points, and 0.61 µg/kg/min, respectively. The mortality of the low T3 and normal T3 groups was similar. Considering the MDN of 0.61 µg/kg/min as the cutoff value, the mortality between the two groups was significantly different. Conclusion: Among patients with sepsis and septic shock, FT3 was inversely correlated with the disease severity. An MDN ≥ 0.61 µg/kg/min within 72 h may be an important prognostic indicator.

Plasmonic evolution of atomically size-selected Au clusters by electron energy loss spectrum.

The plasmonic response of gold clusters with atom number (N) = 100-70 000 was investigated using scanning transmission electron microscopy-electron energy loss spectroscopy. For decreasing N, the bulk plasmon remains unchanged above N = 887 but then disappears, while the surface plasmon firstly redshifts from 2.4 to 2.3 eV above N = 887 before blueshifting towards 2.6 eV down to N = 300, and finally splitting into three fine features. The surface plasmon's excitation ratio is found to follow N 0.669, which is essentially R 2. An atomically precise evolution picture of plasmon physics is thus demonstrated according to three regimes: classical plasmon (N = 887-70 000), quantum confinement corrected plasmon (N = 300-887) and molecule related plasmon (N < 300).

A molecular device providing a remarkable spin filtering effect due to the central molecular stretch caused by lateral zigzag graphene nanoribbon electrodes.

Through the density functional theory, we studied molecular devices composed of single tetrathiafulvalene (TTF) molecules connected with zigzag graphene nanoribbon electrodes by four different junctions. Interestingly, some devices have exhibited half-metallic behavior and can bring out a perfect spin filtering effect and remarkable negative differential resistance behavior. The current-voltage characteristics show that these four devices possess different spin current values. We found that all the TTF molecules were stretched due to interactions with the electrodes in the four devices. This leads to the Fermi levels of the three devices being down-shifted to the valence band; therefore, these devices exhibit half-metallic properties. The underlying mechanisms of the different spin current values are attributed to the different electron transmission pathways (via chemical bonds or through hopping between atoms). These results suggest that the device properties and conductance are controlled by different junctions. Our work predicts an effective way for designing high-performance spin-injected molecular devices.

Highly Promoted Carrier Mobility and Intrinsic Stability by Rolling Up Monolayer Black Phosphorus into Nanoscrolls.

Rolling up two-dimensional (2D) materials into nanoscrolls could not only retain the excellent properties of their 2D hosts but also display intriguing physical and chemical properties that arise from their 1D tubular structures. Here, we report a new class of black phosphorus nanoscrolls (bPNSs), which are stable at room-temperature and energetically more favorable than 2D bP. Most strikingly, these bPNSs hold tunable direct band gaps and extremely high mobilities (e.g., the mobility of the double-layer bPNS is about 20-fold higher than that of 2D bP monolayer). Their unique self-encapsulation structure and layer-dependent conduction band minimum can largely prevent the entrance of O2 and the production of O2- and thereby suppress the possible environmental degradation as well. The enhanced intrinsic stability and promoted electronic properties render bPNSs great promise in many advanced electronics or optoelectronics applications.

Structure and magnetic properties of icosahedral PdxAg13-x (x = 0-13) clusters.

In this article, we present a modified Velocity-Verlet algorithm that makes cluster system converge rapidly and accurately. By combining it with molecular dynamics simulations, we develop an effective global sampling method for extracting isomers of bimetallic clusters. Using this method, we obtain the isomers of icosahedral PdxAg13-x (x = 0-13). Additionally, using the first-principle spin-polarized density functional theory approach, we find that each isomer still retains its icosahedral structure because of strong s-d orbital hybridization, and the cluster is more stable when a Pd atom is at the center of the cluster. With increasing x value, the magnetic moment decreases linearly from 5.0 µB at x = 0, until reaching zero at x = 5, and then increases linearly up to 8.0 µB at x = 13. By calculating the atom-projected density of states (PDOS), we reveal that the magnetic moment of PdxAg13-x mainly originates from s electrons of Ag when 0 ≤ x < 5, and d electrons of Pd when 5 < x ≤ 13. The PDOS results also show that the PdxAg13-x tends to transform from a semiconductor state to semi-metallic state when x gradually increases from 0 to 13.

Controllable Photovoltaic Effect of Microarray Derived from Epitaxial Tetragonal BiFeO3 Films.

Recently, the ferroelectric photovoltaic (FePV) effect has attracted great interest due to its potential in developing optoelectronic devices such as solar cell and electric-optical sensors. It is important for actual applications to realize a controllable photovoltaic process in ferroelectric-based materials. In this work, we prepared well-ordered microarrays based on epitaxially tetragonal BiFeO3 (T-BFO) films by the pulsed laser deposition technique. The polarization-dependent photocurrent image was directly observed by a conductive atomic force microscope under ultraviolet illumination. By choosing a suitable buffer electrode layer and controlling the ferroelectric polarization in the T-BFO layer, we realized the manipulation of the photovoltaic process. Moreover, based on the analysis of the band structure, we revealed the mechanism of manipulating the photovoltaic process and attributed it to the competition between two key factors, i.e., the internal electric field caused by energy band alignments at interfaces and the depolarization field induced by the ferroelectric polarization in T-BFO. This work is very meaningful for deeply understanding the photovoltaic process of BiFeO3-based devices at the microscale and provides us a feasible avenue for developing data storage or logic switching microdevices based on the FePV effect.

Directed growth of graphene nanomesh in purified argon via chemical vapor deposition.

Graphene nanomeshes (GNMs), new graphene nanostructures with tunable bandgaps, are potential building blocks for future electronic or photonic devices, and energy storage and conversion materials. In previous works, GNMs have been successfully prepared on Cu foils by the H2 etching effect. In this paper, we investigated the effect of Ar on the preparation of GNMs, and how the mean density and shape of them vary with growth time. In addition, scanning electron microscopy (SEM) and high resolution transmission electron microscopy (TEM) revealed the typical hexagonal structure of GNM. Atomic force microscopy (AFM) and x-ray photoelectron spectroscopy (XPS) indicated that large copper oxide nanoparticles produced by oxidization in purified Ar can play an essential catalytic role in preparing GNMs. Then, we exhibited the key reaction details for each growth process and proposed a growth mechanism of GNMs in purified Ar.

Nonsequential double ionization with mid-infrared laser fields.

Using a full-dimensional Monte Carlo classical ensemble method, we present a theoretical study of atomic nonsequential double ionization (NSDI) with mid-infrared laser fields, and compare with results from near-infrared laser fields. Unlike single-electron strong-field processes, double ionization shows complex and unexpected interplays between the returning electron and its parent ion core. As a result of these interplays, NSDI for mid-IR fields is dominated by second-returning electron trajectories, instead of first-returning trajectories for near-IR fields. Some complex NSDI channels commonly happen with near-IR fields, such as the recollision-excitation-with-subsequent-ionization (RESI) channel, are virtually shut down by mid-IR fields. Besides, the final energies of the two electrons can be extremely unequal, leading to novel e-e momentum correlation spectra that can be measured experimentally.

Ferroelectric Resistive Switching in High-Density Nanocapacitor Arrays Based on BiFeO3 Ultrathin Films and Ordered Pt Nanoelectrodes.

Ferroelectric resistive switching (RS), manifested as a switchable ferroelectric diode effect, was observed in well-ordered and high-density nanocapacitor arrays based on continuous BiFeO3 (BFO) ultrathin films and isolated Pt nanonelectrodes. The thickness of BFO films and the lateral dimension of Pt electrodes were aggressively scaled down to <10 nm and ∼60 nm, respectively, representing an ultrahigh ferroelectric memory density of ∼100 Gbit/inch(2). Moreover, the RS behavior in those nanocapacitors showed a large ON/OFF ratio (above 10(3)) and a long retention time of over 6,000 s. Our results not only demonstrate for the first time that the switchable ferroelectric diode effect could be realized in BFO films down to <10 nm in thickness, but also suggest the great potentials of those nanocapacitors for applications in high-density data storage.

Local Magnetoelectric Effect in La-Doped BiFeO3 Multiferroic Thin Films Revealed by Magnetic-Field-Assisted Scanning Probe Microscopy.

Multiferroic La-doped BiFeO3 thin films have been prepared by a sol-gel plus spin-coating process, and the local magnetoelectric coupling effect has been investigated by the magnetic-field-assisted scanning probe microscopy connected with a ferroelectric analyzer. The local ferroelectric polarization response to external magnetic fields is observed and a so-called optimized magnetic field of ~40 Oe is obtained, at which the ferroelectric polarization reaches the maximum. Moreover, we carry out the magnetic-field-dependent surface conductivity measurements and illustrate the origin of local magnetoresistance in the La-doped BiFeO3 thin films, which is closely related to the local ferroelectric polarization response to external magnetic fields. This work not only provides a useful technique to characterize the local magnetoelectric coupling for a wide range of multiferroic materials but also is significant for deeply understanding the local multiferroic behaviors in the BiFeO3-based systems.

Transition of recollision trajectories from linear to elliptical polarization.

Using a classical ensemble method, we revisit the topic of recollision and nonsequential double ionization with elliptically polarized laser fields. We focus on how the recollision mechanism transitions from short trajectories with linear polarization to long trajectories with elliptical polarization. We propose how this transition can be observed by meansuring the carrier-envelop-phase dependence of the correlated electron momentum spectra using currently available few-cycle laser pulses.

Electric field control of the magnetic anisotropy energy of double-vacancy graphene decorated by iridium atoms.

To solve the fundamental dilemma in data storage applications, it is crucial to manipulate the magnetic anisotropy energy (MAE). Herein, using first-principles calculations, we predict that the system of double-vacancy graphene decorated by iridium atoms possesses high stability, giant MAE, perpendicular-anisotropy and long-range ferromagnetic coupling. More importantly, the amplitude of MAE can be manipulated by electric fields. This is due to the change in the occupation number of Ir-5d orbitals. The present hybrid system could be a high-performance nanoscale information storage device with ultralow energy consumption.

Polarization-dependent interfacial coupling modulation of ferroelectric photovoltaic effect in PZT-ZnO heterostructures.

Recently, ferroelectric perovskite oxides have drawn much attention due to potential applications in the field of solar energy conversion. However, the power conversion efficiency of ferroelectric photovoltaic effect currently reported is far below the expectable value. One of the crucial problems lies in the two back-to-back Schottky barriers, which are formed at the ferroelectric-electrode interfaces and blocking most of photo-generated carriers to reach the outside circuit. Herein, we develop a new approach to enhance the ferroelectric photovoltaic effect by introducing the polarization-dependent interfacial coupling effect. Through inserting a semiconductor ZnO layer with spontaneous polarization into the ferroelectric ITO/PZT/Au film, a p-n junction with strong polarization-dependent interfacial coupling effect is formed. The power conversion efficiency of the heterostructure is improved by nearly two orders of magnitude and the polarization modulation ratio is increased about four times. It is demonstrated that the polarization-dependent interfacial coupling effect can give rise to a great change in band structure of the heterostructure, not only producing an aligned internal electric field but also tuning both depletion layer width and potential barrier height at PZT-ZnO interface. This work provides an efficient way in developing highly efficient ferroelectric-based solar cells and novel optoelectronic memory devices.

High-temperature quantum anomalous Hall effect in honeycomb bilayer consisting of Au atoms and single-vacancy graphene.

The quantum anomalous Hall effect (QAHE) is predicted to be realized at high temperature in a honeycomb bilayer consisting of Au atoms and single-vacancy graphene (Au2-SVG) based on the first-principles calculations. We demonstrate that the ferromagnetic state in the Au2-SVG can be maintained up to 380 K. The combination of spatial inversion symmetry and the strong SOC introduced by the Au atoms causes a topologically nontrivial band gap as large as 36 meV and a QAHE state with Chern number C = -2. The analysis of the binding energy proved that the honeycomb bilayer is stable and feasible to be fabricated in experiment. The QAHEs in Ta2-SVG and other TM2-SVGs are also discussed.

Solvothermal Synthesis of Lateral Heterojunction Sb2Te3/Bi2Te3 Nanoplates.

A lateral heterojunction of topological insulator Sb2Te3/Bi2Te3 was successfully synthesized using a two-step solvothermal method. The two crystalline components were separated well by a sharp lattice-matched interface when the optimized procedure was used. Inspecting the heterojunction using high-resolution transmission electron microscopy showed that epitaxial growth occurred along the horizontal plane. The semiconducting temperature-resistance curve and crossjunction rectification were observed, which reveal a staggered-gap lateral heterojunction with a small junction voltage. Quantum correction from the weak antilocalization reveals the well-maintained transport of the topological surface state. This is appealing for a platform for spin filters and one-dimensional topological interface states.