Electron-phonon coupling, bipolar effects, and thermoelectric performance of the CuSbS2 monolayer.

The thermoelectric performance of the CuSbS2 monolayer is determined using the relaxation times obtained from electron-phonon coupling calculations and the transport properties of phonons and electrons. Based on the fully relaxed structure, the lattice thermal conductivity and the electronic transport coefficients are evaluated by solving the Boltzmann transport equation for phonons and electrons under relaxation time approximation, respectively. The tendencies of the transport coefficients depending on the carrier concentrations and temperatures are studied to understand the thermoelectric performance. Based on the bipolar effect, the transport coefficients and intrinsic carrier concentrations, we determined the dimensionless figure of merit ZT in the 300-800 K range. The results demonstrate that the CuSbS2 monolayer should be an p-type semiconductor, and the maximum ZT of 1.36 is obtained, indicating that the monolayer is a good candidate for high-temperature thermoelectric devices. Substantial bipolar effects are observed, and the ones in the x-direction are stronger in comparison to those in the y-direction, which is responsible for the smaller ZT in the x-direction.

Efficient photocatalytic hydrogen evolution and CO2 reduction by HfSe2/GaAs3 and ZrSe2/GaAs3 heterostructures with direct Z-schemes.

The elaborate configuration of the heterostructure is crucial and challenging to achieve high solar-to-hydrogen efficiency or CO2 reduction efficiency . Here, we predict two heterostructures composed of HfSe2, ZrSe2, and GaAs3 monolayers. The maximum of 42.71%/35.12% with the heterostructures can be reached with the perfect match between the bandgap and band edges. The configurations of the heterostructures are discovered from 12 possible stacking types of the three monolayers. The formation energy, potentials of band edges, carrier mobilities, and optical absorption were used to identify the feasibility of the CO2 reduction reaction (CO2RR), the hydrogen evolution reaction (HER), and the oxygen evolution reaction (OER). The and based on overpotentials and bandgaps and the Gibbs free energies (ΔGs) are evaluated to quantificationally access the photocatalytic performance of the constructed heterostructures. The results demonstrate that high can be obtained for the solar photocatalytic Z-schemes with the HfSe2/GaAs3 and ZrSe2/GaAs3 heterostructures, and these values can be further enhanced through strain engineering. Moreover, small changes in ΔGs were observed for HER, OER, and CO2RR. Therefore, the two heterostructures have excellent performance in photocatalytic hydrogen evolution and CO2 reduction. The results of the electronic properties revealed that the delicate matching of the projected band edges of the monolayers in the heterostructures is responsible for the high photocatalytic performance.

Formation of stable aggregates by fluid-assembled solid bridges.

When a colloidal suspension is dried, capillary pressure may overwhelm repulsive electrostatic forces, assembling aggregates that are out of thermal equilibrium. This poorly understood process confers cohesive strength to many geological and industrial materials. Here we observe evaporation-driven aggregation of natural and synthesized particulates, probe their stability under rewetting, and measure bonding strength using an atomic force microscope. Cohesion arises at a common length scale (∼5 µm), where interparticle attractive forces exceed particle weight. In polydisperse mixtures, smaller particles condense within shrinking capillary bridges to build stabilizing "solid bridges" among larger grains. This dynamic repeats across scales, forming remarkably strong, hierarchical clusters, whose cohesion derives from grain size rather than mineralogy. These results may help toward understanding the strength and erodibility of natural soils, and other polydisperse particulates that experience transient hydrodynamic forces.

Opposite Sensing Response of Heterojunction Gas Sensors Based on SnO2-Cr2O3 Nanocomposites to H2 against CO and Its Selectivity Mechanism.

Metal oxide semiconductor (MOS) gas sensors show poor selectivity when exposed to mixed gases. This is a challenge in gas sensors and limits their wide applications. There is no efficient way to detect a specific gas when two homogeneous gases are concurrently exposed to sensing materials. The p-n nanojunction of xSnO2-yCr2O3 nanocomposites (NCs) are prepared and used as sensing materials (x/y shows the Sn/Cr molar ratio in the SnO2-Cr2O3 composite and is marked as SnxCry for simplicity). The gas sensing properties, crystal structure, morphology, and chemical states are characterized by employing an electrochemical workstation, an X-ray diffractometer, a transmission electron microscope, and an X-ray photoelectron spectrometer, respectively. The gas sensing results indicate that SnxCry NCs with x/y greater than 0.07 demonstrate a p-type behavior to both CO and H2, whereas the SnxCry NCs with x/y < 0.07 illustrate an n-type behavior to the aforementioned reduced gases. Interestingly, the SnxCry NCs with x/y = 0.07 show an n-type behavior to H2 but a p-type to CO. The effect of the operating temperature on the opposite sensing response of the fabricated sensors has been investigated. Most importantly, the mechanism of selectivity opposite sensing response is proposed using the aforementioned characterization techniques. This paper proposes a promising strategy to overcome the drawback of low selectivity of this type of sensor.

The high power conversion efficiency of a two-dimensional GeSe/AsP van der Waals heterostructure for solar energy cells.

Constructing a van der Waals heterostructure is a practical way to promote the conversion efficiency of solar energy. Here, we demonstrate the efficient performance of a GeSe/AsP heterostructure in solar energy cells based on the first-principles calculations. The electronic properties, optical absorption, and optoelectronic properties are calculated to evaluate the efficiency of the newly designed heterostructure. The results indicate that the GeSe/AsP heterostructure possesses a type-II band alignment with an indirect bandgap of 1.10 eV, which greatly promotes the effective separation of photogenerated carriers. Besides, an intrinsic electric field is formed in the direction from the AsP to GeSe monolayer, which is beneficial to prevent the recombination of the photogenerated electron-hole pair. Simultaneously, a strong optical absorption is observed in the visible light range. The predicted power conversion efficiency (PCE) of the GeSe/AsP heterostructure is 16.0% and can be promoted to 17.3% by applying 1% biaxial compression strain. The present results indicate that the GeSe/AsP heterostructure is a promising candidate material for high-performance solar cells.

Direct laser cooling schemes for the triatomic SOH and SeOH molecules based on ab initio electronic properties.

Direct laser cooling is a very promising method to obtain cold molecules for various applications. However, a molecule with satisfactory electronic and optical properties for the optical scheme is difficult to identify. By suggesting criteria for the qualified molecules, we develop a method to identify the suitable polyatomic molecules for direct laser cooling. The new criteria from the equilibrium geometrical structures and fundamental frequencies of the ground and low-lying excited states are used to replace the past ones based on Franck-Condon factors. The new method can rapidly identify the preferable one among many candidate polyatomic molecules based on ab initio calculations because the new criteria are free from the construction of potential energy surfaces. The method is testified by using triatomic molecules containing OH. All the reported and two new molecules suitable for direct laser cooling are identified by comparing 168 electronic states of 28 molecules with the new criteria. The newly found molecules have been confirmed using the Franck-Condon factors from the construction of potential energy surfaces. Finally, the optical schemes for the direct laser cooling of the SOH and SeOH molecules are established.

Preparation and fluorescence characterization of monodisperse core-shell structure SiO2 @SiO2 :Tb(1,2-BDC)3 phen microspheres by a sol-seed method.

The SiO2 @SiO2 :Tb(1,2-BDC)3 phen microspheres with monodispersed core-shell structure, are kind of fluorescent particles, which are prepared by a seeded growth method under the catalysis of glacial acetic acid (1,2-BDC, 1,2-benzenedicarboxylic acid; phen, 1,10-phenanthroline). Firstly, silica seed was fabricated by the hydrolysis of ethyl orthosilicate, and the Tb(1,2-BDC)3 phen was prepared by using 1,2-BDC and phen. Then, a thin mesoporous silica shell doped with Tb(1,2-BDC)3 phen was grown on the prepared monodisperse silica colloids. The prepared phosphor was analyzed by Fourier-transform infrared spectroscopy, X-ray diffraction analysis, scanning electron microscopy, transmission electron microscopy, thermogravimetric and fluorescence spectroscopy. The experimental results showed that the diameter of the SiO2 @SiO2 :Tb((1,2-BDC)3 phen microsphere was about 200 nm with a typical core-shell structure, among which the diameter of the silica core was 180 nm, and that of the mesoporous silicon shell doped with terbium complex was about 10 nm. The fluorescence intensity of SiO2 @SiO2 :Tb((1,2-BDC)3 phen microsphere is nearly three times higher than that of Tb((1,2-BDC)3 phen complexes. The prepared microspheres could be widely used in bio-imaging, optoelectronic appliances and medical diagnosis.

Colloidal diffusion over a quenched two-dimensional random potential.

A two-layer colloidal system is developed for the study of diffusion over a quenched two-dimensional random potential. A mixture of bidisperse silica spheres is used to form a randomly packed colloidal monolayer on the bottom substrate. The corrugated surface of the bottom colloidal monolayer provides a gravitational potential field for the dilute diffusing particles in the top layer. The population probability histogram P(x,y) of the diffusing particles is obtained to fully characterize the random potential landscape U(x,y) via the Boltzmann distribution. The dynamical properties of the top diffusing particles, such as their mean square displacement (MSD), histogram of the escape time, and long-time self-diffusion coefficient, are simultaneously measured from the particle trajectories. A quantitative relationship between the long-time diffusion coefficient and the random potential is obtained, which is in good agreement with the theoretical prediction. The measured MSD reveals a wide region of subdiffusion resulting from the structural disorders. The crossover from subdiffusion to normal diffusion is explained by the Lorentz model for tracer diffusion through a heterogeneous space filled with a set of randomly distributed obstacles.

Ab initio studies on the spin-forbidden cooling transitions of the LiRb molecule.

The spin-forbidden cooling of the LiRb molecule is investigated based on ab initio quantum chemistry calculations. The multireference configuration interaction method is used to generate the potential energy curves (PECs) of the ground state X(1)Σ(+) and the low-lying excited states a(3)Σ(+), B(1)Π, and b(3)Π. The spin-orbit coupling effects for the PECs and the transition dipole moments (TDMs) between the X(1)Σ(+), b(3)Π and a(3)Σ(+) states are also calculated. The analytical functions for the PECs are deduced. The rovibrational energy levels, the spectroscopic parameters and the Franck-Condon factors (FCF) are determined by solving the Schrödinger equation of nuclear movement with the obtained analytical functions. The b(3)Π0 ↔ X(1)Σ(+) and b(3)Π1 ↔ X(1)Σ(+) transitions have highly diagonal distributed FCFs and non-zero TDMs, demonstrating that the LiRb molecule could be a very promising candidate for laser cooling. Therefore, a three-cycle laser cooling scheme for the molecule has been proposed based on these two spin-forbidden transitions. Using the radiative lifetime and linewidth calculated from the obtained TDM functions, we present further analysis of the cooling of LiRb and the corresponding KRb molecule. The transition b(3)Π0 ↔ X(1)Σ(+) is found to be a practical transition to cool the LiRb molecule, and a sub-microkelvin cool temperature could be reached for the KRb molecule using a similar laser cooling scheme.

Colloidal transport and diffusion over a tilted periodic potential: dynamics of individual particles.

A tilted two-layer colloidal system is constructed for the study of force-assisted barrier-crossing dynamics over a periodic potential. The periodic potential is provided by the bottom layer colloidal spheres forming a fixed crystalline pattern on a glass substrate. The corrugated surface of the bottom colloidal crystal provides a gravitational potential field for the top layer diffusing particles. By tilting the sample at an angle θ with respect to the vertical (gravity) direction, a tangential component of the gravitational force F is applied to the diffusing particles. The measured mean drift velocity v(F, Eb) and diffusion coefficient D(F, Eb) of the particles as a function of F and energy barrier height Eb agree well with the exact results of the one-dimensional drift velocity (R. L. Stratonovich, Radiotekh. Elektron, 1958, 3, 497) and diffusion coefficient (P. Reimann, et al., Phys. Rev. Lett., 2001, 87, 010602 and P. Reimann, et al., Phys. Rev. E, 2002, 65, 031104). Based on these exact results, we show analytically and verify experimentally that there exists a scaling region, in which v(F, Eb) and D(F, Eb) both scale as ν'(F)exp[-E(F)/kBT], where the Arrhenius pre-factor ν'(F) and effective barrier height E(F) are both modified by F. The experiment demonstrates the applications of this model system in evaluating different scaling forms of ν'(F) and E(F) and their accuracy, in order to extract useful information about the external potential, such as the intrinsic barrier height Eb.

Dietary Patterns Associated Metabolic Syndrome in Chinese Adults.

Dietary pattern has been revealed to be associated with metabolic syndrome. However, the association was not well documented in Chinese due to the complexity of Chinese foods. We mainly assessed the dietary patterns and examined their effects on metabolic syndrome among Chinese adults. Four dietary patterns including 'Refined Grains & Vegetables' Pattern, 'Dairy & Eggs' Pattern, 'Organ Meat & Poultry' Pattern, and 'Coarse Grains & Beans' Pattern were extracted. 'Dairy & Eggs' Pattern was associated with a decreased odds of metabolic syndrome in women, and 'Coarse Grains & Beans' Pattern was associated with a decreased odds of hypertension in men. These results provided a scientific basis for future research and dietary guideline perfection.

Ab initio study on the ground and low-lying states of BAlk (Alk = Li, Na, K) molecules.

The potential energy curves (PECs) and dipole moment functions of (1)Π, (3)Π, (1)Σ(+), and (3)Σ(+) states of BAlk (Alk = Li, Na, K) are calculated using multireference configuration interaction method and large all-electron basis sets. The effects of inner-shell correlation electron for BAlk are considered. The ro-vibrational energy levels are obtained by solving the Schrödinger equation of nuclear motion based on the ab initio PECs. The spectroscopic parameters are determined from the ro-vibrational levels with Dunham expansion. The PECs are fitted into analytical potential energy functions using the Morse long-range potential function. The dipole moment functions for the states of BAlk are presented. The transition dipole moments for (1)Σ(+) → (1)Π and (3)Σ(+) → (3)Π states of BAlk are obtained. The interactions between the outermost electron of Alk and B 2p electrons for (1)Π, (3)Π, (1)Σ(+), and (3)Σ(+) states are also analyzed, respectively.

Quasi-classical trajectory study of the N(2D) + H2(X1ΣG+) → NH(X3Σ-) + H(2S) reaction based on an analytical potential energy surface.

Using the multireference configuration interaction method with the Davidson correction and a large orbital basis set (aug-cc-pV5Z), we obtain an energy grid that includes 17,500 points for the construction of a new analytical potential energy surface (APES) for the N((2)D) + H(2)(X(1)Σ(g)(+)) → NH(X(3)Σ(-)) + H((2)S) reaction. The APES, which contains 145 parameters and is represented with a many-body expansion and a new switch function, is fitted from the ab initio energies using an adaptive nonlinear least-squares algorithm. The geometric characteristics of the reported APES in the literature and those of our APES are also compared. On the basis of the APES that we obtained, reaction cross sections are computed by means of quasi-classical trajectory calculations and compared with the experimental and theoretical values available in the literature.

An ab initio study of the ground and low-lying excited states of KBe with the effect of inner-shell electrons.

The potential energy curves (PECs) of 1(2)Σ(+), 2(2)Σ(+), 1(2)Π, and 2(2)Π states of KBe are calculated using multireference configuration interaction method and large all-electron basis sets. Four sets of frozen core orbitals (FCOs) are considered to examine the effect of inner-shell correlation electrons on the molecular properties. The ro-vibrational energy levels are obtained by solving the Schrödinger equation of nuclear motion based on the ab initio PECs. The spectroscopic parameters are determined from the ro-vibrational levels with Dunham expansion. The PECs are fitted into analytical potential energy functions using the Morse long-range potential function. The dipole moment functions of the states for KBe calculated with different FCOs are presented. The transition dipole moments for KBe between 1(2)Σ(+) and 2(2)Σ(+) states, 1(2)Π and 1(2)Σ(+) states, and 2(2)Π and 1(2)Σ(+) states are also obtained.

Insights into Photogenerated Carrier Dynamics and Overall Water Splitting of the CrS3/GeSe Heterostructure.

Based on the nonadiabatic molecular dynamics (NAMD) simulations and the first-principles calculations, we explore the overall water-splitting schemes and the photogenerated carrier dynamics for two configurations (CG and CyG) of the CrS3/GeSe van der Waals heterostructures. The photocatalytic direct Z-schemes and carrier migration pathways for hydrogen and oxygen evolution reactions (HER/OER) are constructed based on the electronic properties. The solar-to-hydrogen efficiency (η'STH values) of the schemes can reach 10.60% and 10.17% and further rise under tensile strain. The NAMD results demonstrate similar transfer times of the electron/hole for HER/OER and more rapid electron-hole recombination in CG enables it to be superior to CyG in photocatalytic performance. Moreover, the Gibbs free energy indicates that both the HERs and OERs turn to spontaneously proceed with CG and CyG at pH = 0-12.37 and pH = 2.55-11.01, respectively. These facts reveal that the CrS3/GeSe heterostructure is promising in photocatalytic overall water splitting.

2D XBiSe3(X = Ga, In, Tl) monolayers with high carrier mobility and enhanced visible-light absorption.

The geometrical configurations of the XBiSe3 (X = Ga, In, Tl) monolayers are identified by employing the first-principles density functional theory calculations, and the stabilities are confirmed by phonon dispersion, formation energy, and ab initio molecular dynamics simulation, respectively. The bandgap and band edges, the density of states, the optical absorption, mobility, and effect of strain engineering are evaluated to understand the photoelectronic properties of the monolayers. The results show that the XBiSe3 monolayers have the indirect bandgaps of 1.14-1.69 (1.20-1.84) eV by HSE06(GW), leading to the enhanced optical absorption from the visible to near-ultraviolet region. The large mobility of the electron and hole are also observed, which is helpful for the separation and transfer of the photogenerated carrier pair. The band edges and bandgaps, as well as the optical absorptions, can effectively be tuned by strain engineering. It should be noted that the band edges of the InBiSe3 monolayer could satisfy the condition of redox potential for the hydrogen evolution reaction under the compressive strain heavier than -3%, implicating this monolayer can also be used for photocatalytic water splitting to produce hydrogen. Therefore, these monolayers have potential applications in photocatalytic materials or photoelectronic devices such as energy harvesters and visible-light sensors.

Crystallization of alkane melts induced by carbon nanotubes and graphene nanosheets: a molecular dynamics simulation study.

The crystallization of alkane melts on carbon nanotubes (CNT) and the surface of graphene nanosheets (GNS) is investigated using molecular dynamics (MD) simulations. The crystallization process of the alkane melts is analyzed in terms of the bond-orientational order parameter, atomic radial distribution for the CNT/alkane, atomic longitudinal distribution for the GNS/alkane, and diffusion properties. The dimensional effects of the different carbon-based nanostructures on the crystallization of alkane melts are shown. It is found that one-dimensional CNT has a stronger ability to induce the crystallization of the polymer than that of two-dimensional GNS, which provides a support at molecular level for the experimental observation [Li et al., J. Am. Chem. Soc., 2006, 128, 1692 and Xu et al., Macromolecules, 2010, 43, 5000]. From the MD simulations, we also find that the crystallization of alkane molecules has been completed with the highly cooperative processes of adsorption and orientation.

Quasi-classical trajectory study of the Ne + H2(+) → NeH(+) + H reaction based on global potential energy surface.

Using the multireference configuration interaction method with a Davidson correction and a large orbital basis set (aug-cc-pVQZ), we obtain an energy grid that includes 32 038 points for the construction of a new analytical potential energy surface (APES) for the Ne + H(2)(+) → NeH(+) + H reaction. The APES is represented as a many-body expansion containing 142 parameters, which are fitted from 31 000 ab initio energies using an adaptive nonlinear least-squares algorithm. The geometric characteristics of the reported APES and the one presented here are also compared. On the basis of the APES we obtained, reaction cross sections are computed by means of quasi-classical trajectory (QCT) calculations and compared with the experimental and theoretical data in the literature.

Interactions of M(z)-X complexes (M = Cu, Ag, and Au; X = He, Ne, and Ar; and z = ±1).

The coupled cluster singles and doubles method with perturbative treatment of triple excitations is applied to calculate the potentials of M(z)-X complexes (M = Cu, Ag, and Au; X = He, Ne, and Ar; and z = ±1). The bond functions and the basis set superposition errors are considered to obtain accurate interaction energies. The potential energy curves of all complexes are obtained. The vibrational energy levels and the spectroscopic parameters for these complexes are determined. The analytical potential energy functions are also fitted based on the potential energies.

A retrospective study of q-switched alexandrite laser in treating nevus of ota.

BACKGROUND: The Q-switched alexandrite laser (QSAL) has been clinically proven to be effective in treating nevus of Ota, but a large-scale retrospective study with long-term follow-up has never been performed. OBJECTIVE: To evaluate the efficacy of the QSAL in treating nevus of Ota, the laser's long-term side effects, complications associated with the treatments, and the recurrence rate. MATERIALS AND METHODS: Eight hundred six patients (651 female, 155 male) with a diagnosis of nevus of Ota who had received a series of QSAL (wavelength 755 nm) treatments were recruited. The typical settings were fluences of 3.8 to 4.8 J/cm(2) and a spot size of 3 mm. Follow-ups were conducted via questionnaire with 590 patients who had completed the treatment at least 3 years earlier. RESULTS: Overall, 93.9% of patients achieved complete clearance after an average of 5.2 sessions. All recurrences (0.8%) appeared beyond the previously treated sites. No long-term adverse effects, including hypopigmentation, hyperpigmentation, textural changes, and malignant transformation, were observed. CONCLUSION: The QSAL is a safe and effective modality for treating nevus of Ota. Recurrence was rare and appeared beyond the previously treated sites. The authors have indicated no significant interest with commercial supporters.