STM study of di-indenoperylene molecules on Cu(1 0 0) surfaces: Mobility, stability and epitaxy

We report a detailed study of the self-assembly process of di-indenoperylene (DIP) on Cu(1 0 0) surfaces, investigated by variable temperature scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV) conditions. During the initial growth stages a preferred nucleation at the step edges is revealed. Subsequently, large ordered 2D islands grow from the step edges, while smaller 2D islands form on the terrace sites. The equilibrium fluctuation of these 2D clusters has been monitored in real-time, thereby obtaining a direct insight into the temperature dependence of the molecular surface diffusion. The substrate–adsorbate interactions determine the azimuthal molecular orientation, finally lead to the formation of highly ordered chiral domains which are commensurate with the substrate.     

Insight into STM image contrast of n-tetradecane and n-hexadecane molecules on highly oriented pyrolytic graphite

Two-dimensional ordered patterns of n-tetradecane (n-C₁₄H₃₀) and n-hexadecane (n-C₁₆H₃₄) molecules at liquid/graphite interface have been directly imaged using scanning tunneling microscope (STM) under ambient conditions. STM images reveal that the two different kinds of molecules self-organize into ordered lamellar structures in which alkane chains of the molecules extend along one of three equivalent lattice axes of highly oriented pyrolytic graphite (HOPG) basal plane. For n-C₁₄H₃₀ molecules, the molecular axes are observed to tilt by 60° with respect to inter-lamellar trough lines and the carbon backbones of the alkane chains are perpendicular to the HOPG basal plane in an all-trans conformation. However, for n-C₁₆H₃₄ molecules, the molecular axes are perpendicular to lamellar borders (90°) and the planes of the all-trans carbon skeletons are parallel to the graphite basal plane. The results clearly indicate that outmost hydrogen atoms of the alkane chains dominate atom-scaled features of the STM images. That is, in the case of long-chain alkane molecules, topographic effects dominantly determine STM image contrast of the methylene regions of the alkane chains that are adsorbed on HOPG.     

Weak dependence of spontaneous polarization on epitaxial strain in ferroelectric BiAlO3: A first-principles study

We investigate the effects of epitaxial strain on the ferroelectric properties of BiAlO₃ (BAO) using first-principles calculations. We find a large polarization (P) of 72.3 μC/cm² as well as a small energy barrier of ∼0.1 eV/formula unit for coherent ferroelectric switching of unstrained BAO. Thus, this material is suitable for applications in high-speed nonvolatile memory. We study the modification of P due to epitaxial strains of −5 to +5%, where the minus and plus signs represent the compressive and tensile strains, respectively. The polarization of BAO is insensitive to epitaxial strain; the polarization change is limited to below ∼6%. The weak sensitivity of the polarization is attributed to the stereochemical activity of Bi 6s² lone pairs as well as the inertness of the B-site Al to the polarization. The strain application modifies the switching energy barrier by up to 30%, which provides guidelines for design of devices based on BAO.     

基于第一性原理计算Mn掺杂MoS2对油中溶解气体的吸附性能

CO、C₂H₂、CH₄是溶解在变压器油中的典型故障特征气体,其种类和浓度能够反映油浸式变压器绝缘故障的不同类型和严重程度,进行油中溶解气体分析是在线检测变压器运行状态的重要方法.基于第一性原理,通过Mn-MoS₂单层对三种气体的吸附能、转移电荷、态密度和形变电荷密度等参数以及解吸性能分析和灵敏度计算,提出了一种基于Mn-MoS₂材料的气敏传感器对油中溶解气体进行分析的方法.结果表明Mn-MoS₂对CH₄是物理吸附,对CO和C₂H₂是化学吸附.对于Mn-MoS₂来说,CH₄在常温下吸附能力差且灵敏度低,CO在不同温度下均有较强的吸附能力,而C₂H₂在常温下吸附稳定,高温下易解吸且响应灵敏度高.因此,Mn掺杂的MoS₂体系可预期作为CO的气体吸附剂和检测C₂H     

Doping level and environment dependence of structural stability and magnetic properties in Mn-doped WS2 bilayer in first principles

We carried out first-principles electronic structure calculation to study the structural stability and magnetic properties of Mn-doped WS₂ ultra-thin films within the density functional theory. Adopting various configurations of Mn doping into WS₂ bilayer, we find that the magnetic phase can be manipulated among the ferromagnetic, antiferromagnetic, or ferrimagnetic phases by altering doping level and growth environment. Magnetic phase and strength are determined by magnetic coupling of Mn dopants 3d electrons which can be attributed crucially to the exchange interaction mediated by neighboring S atoms 3p electrons. Accompanying to the magnetic phase transition, the electronic structure reveals that transport properties switch from semiconducting with various bandgap to half-metallic states. This result implicates possible way to develop magnetic semiconductors based on Mn doped 2D WS₂ ultra-thin films for spintronics applications.     

The dependence of relaxation rates and chemical shift on the size of the imaged molecules and the concentration of MRI contrast agents

An intriguing phenomenon on enhancement of the relaxation rates and chemical shift of two typical magnetic resonance imaging (MRI) contrast agents based on gadolinium complex is observed. The relaxation enhancement or chemical shift change depends on the size of the molecule where the imaged nuclear species is located: the small molecules show a perfect linear relationship between the concentration and the relaxation enhancement or chemical shift change while for macromolecules pronounced nonlinearity is observed. The phenomenon is also confirmed with real images of a macromolecular sample. A quantitative theoretical interpretation of the phenomenon is proposed and the significance of this phenomenon to MRI of materials and biological systems is discussed.     

Freezing of phase separation in spatiotemporal stripe patterns formed by Ag and Sb co-electrodeposition

Various spatiotemporal patterns of dark and light stripes are formed in the Ag and Sb co-electrodeposition system. In this research, we investigate the time-evolution of the stripe width of a spatiotemporal stripe pattern with a size of ca. 10 μm. The results show that the stripe width increases with time and is eventually saturated. Such a phenomenon is predicted by some theories of spinodal decomposition of materials with chemical reactions in a nonequilibrium system. This suggests that the pattern is formed by the spinodal decomposition of metal alloys, Ag and Sb, with chemical reactions in a nonequilibrium system, which has not yet been reported in a metallic system.     

Orientational effects in the energy dependence of the reaction cross-section from model calculations

Summary A dynamical model to calculate the kinetic-energy dependence of the reaction cross-section is presented. The most important aspects of the present treatment area) an orientational dependence of the reaction barrier,b) the onset of a recrossing mechanism andc) the operation of alignment forces during the reaction time. Application to several reactions of oriented or nonoriented reactants’ geometry gives a satisfactory fit of the excitation function data providing a clear insight into the diagnosis of the reaction dynamics that governs the reactive collision.

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Riassunto Si presenta un modello dinamico per calcolare la dipendenza dall’energia cinetica della sezione d’urto della reazione. Gli aspetti piú importanti di questo modello sono:a) una dipendenza orientazionale della barriera di reazione,b) l’insorgenza di un meccanismo di reincrocio ec) l’intervento di forze di allineamento durante il tempo di reazione. L’applicazione a parecchie reazioni con geometria dei reagenti orientata o non orientata dà un’approssimazione soddisfacente dei dati della funzione di eccitazione fornendo una chiara visione della diagnosi della dinamica di reazione che controlla la collisione reattiva.

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Резюме Предлагается динамическая модель для вычисления зависимости поперечного сечения реакции от кинетической знергии. Наиболее важные аспекты предлагаемого подхода: 1) ориентационная зависимость барьера реакции; 2) возникновение механизма пересечения; 3) действие сил ориентации во время реакции. Примение предложенного подхода к некоторым реакциям в случае ориентированной или неориентированной геометрии реагентов дает удовлетворительное соответствие с имеюцимися данными и обеспечивает правильное представление диагностики динамики реакции, которая определяет процесс соударения.