A PBC‐DFT study of electronic properties of substituted polythiophenes

The electronic properties of polythiophenes substituted with various electron‐withdrawing and electron‐donating groups are investigated by employing periodic density functional calculations. The polymer is modeled as infinite one‐dimensional system with periodic boundary condition along the molecular direction. The effect of substitution on bandgaps is studied with various substituents like alkyls, halogens, aromatic and alkoxy groups in different regioregular forms. The alkoxy groups are found to substantially lower the bandgap of unsubstituted polythiophene, and aromatic groups in head–head/tail–tail forms are found to increase the bandgap. Irrespective of the type of substituents, groups that show deviations in planarity in oligomeric forms have shown an increase in bandgap in contrast to the general perception that head–head linkage always results in an increase in bandgap. Our study also confirms the previous findings that scaling from the oligomer bandgaps poses serious limitation to the prediction of polymeric bandgaps and that it should be evaluated with the infinite polymer system employing periodic boundary condition. Copyright © 2015 John Wiley & Sons, Ltd.     

On the entropic nucleation barrier in a martensitic transformation

The nucleation of martensite in alloys is hindered by a free energy nucleation barrier, hence comprising contributions of the potential energy and the entropy. The leading effect is commonly attributed to the potential energy barrier due to strain fields. In this contribution, we investigate the nature of the entropic barrier by means of molecular dynamics (MD) simulations. We study a transformation process of an undercooled single crystal and examine two nucleation events observed under adiabatic conditions using vibrational mode analysis of the atomic trajectories. Our analysis shows that martensitic nucleations are indicated by transit from a state of uncorrelated into a state of correlated atomic motions. This correlation process is built up locally by a small group of atoms even before the product lattice can be recognized morphologically and it produces vibrational ‘soft’ modes along transformation paths. Phase space analyses unveil that the correlation process is characterized by narrow domains – ‘nucleation channels’ – the atomic trajectories have to pass, connecting the phase space domains of the parent and the product lattice. For a successful nucleation event, the nucleus atoms have to pass this channel collectively, which stochastically represents a rare event. Thermal fluctuations prevent finding the channel at elevated temperature and give rise for entropic stabilization of the parent phase. This ‘entropic nucleation barrier’ is reduced in the undercooled state but still effective, thus preventing the parent phase from collapsing into the product. The entropic barrier may be interpreted as the probability of a group of atoms to simultaneously pass the nucleation channel. Such group then represents a nucleus.     

A novel nanoscale fin field effect transistor by amended channel: Investigation and fundamental physics

The present paper proposes a new Fin Field Effect Transistor (FinFET) with an amended Channel (AC). The fin region consists of two sections; the lower part which has a rounded shape and the upper part of fin as conventional FinFETs, is cubic. The AC-FinFET devices are proven to have a lower threshold voltage roll-off, reduced DIBL, better subthreshold slope characteristics, and a better gate capacitance in comparison with the C-FinFET. Moreover, the simulation result with three-dimensional and two-carrier device simulator demonstrates an improved output characteristic of the proposed structure due to reduction of self-heating effect. Due to the rounded shape of the lower fin region and decreasing corner effects there, the heat can flow easily, and the device temperature will decrease. Also the gate control over the channel increases due to the narrow upper part of the fin. The paper, thus, attempts to show the advantages of higher performance AC-FinFET device over the conventional one, and its effect on the operation of nanoscale devices.     

Vesicle Structures from Bolaamphiphilic Biosurfactants: Experimental and Molecular Dynamics Simulation Studies on the Effect of Unsaturation on Sophorolipid Self‐Assemblies

The formation of giant‐vesicle‐like structures by self‐assembling linolenic acid sophorolipid (LNSL) molecules is revealed. Sophorolipids belong to the class of bolaamphiphilic glycolipid biosurfactants. Interestingly, the number of double bonds present in the hydrophobic core of sophorolipids is seen to have a great influence on the type of self‐assembled structures formed. Dye encapsulation results establish the presence of an aqueous compartment inside the LNSL vesicles. Molecular dynamics simulation (MD) studies suggest the existence of two possible conformations of LNSLs inside the self‐assembled structures and that LNSL molecules arrange in layered structures.     

A Novel Bismuth‐Based Metal–Organic Framework for High Volumetric Methane and Carbon Dioxide Adsorption

Solvothermal reaction of H₄L (L=biphenyl‐3,3′,5,5′‐tetracarboxylate) and Bi(NO₃)₃ ? (H₂O)₅ in a mixture of DMF/MeCN/H₂O in the presence of piperazine and nitric acid at 100 °C for 10 h affords the solvated metal–organic polymer [Bi₂(L)_1.5(H₂O)₂] ? (DMF)_3.5 ? (H₂O)₃ (NOTT‐220‐solv). A single crystal X‐ray structure determination confirms that it crystallises in space group P2/c and has a neutral and non‐interpenetrated structure comprising binuclear {Bi₂} centres bridged by tetracarboxylate ligands. NOTT‐220‐solv shows a 3,6‐connected network having a framework topology with a {4 ? 6²}₂{4² ? 6⁵ ? 8⁸}{6² ? 8} point symbol. The desolvated material NOTT‐220a shows exceptionally high adsorption uptakes for CH₄ and CO₂ on a volumetric basis at moderate pressures and temperatures with a CO₂ uptake of 553 g L^?1 (20 bar, 293 K) with a saturation uptake of 688 g L^?1 (1 bar, 195 K). The corresponding CH₄ uptake was measured as 165 V(STP)/V (20 bar, 293 K) and 189 V(STP/V) (35 bar, 293 K) with a maximum CH₄ uptake for NOTT‐220a recorded at 20 bar and 195 K to be 287 V(STP)/V, while H₂ uptake of NOTT‐220a at 20 bar, 77 K is 42 g L^?1. These gas uptakes have been modelled by grand canonical Monte Carlo (GCMC) and density functional theory (DFT) calculations, which confirm the experimental data and give insights into the nature of the binding sites of CH₄ and CO₂ in this porous hybrid material.     

Separation of micro and sub-micro diamagnetic particles in dual ferrofluid streams based on negative magnetophoresis

In the present study, we numerically demonstrate an approach for separation of micro and sub-micro diamagnetic particles in dual ferrofluid streams based on negative magnetophoresis. The dual streams are constructed by an intermediate sheath flow, after which the negative magnetophoretic force induced by an array of permanent magnets dominates the separation of diamagnetic particles. A simple and efficient numerical model is developed to calculate the motions of particles under the action of magnetic field and flow field. Effects of the average flow velocity, the ratio of sheath fluid flow to sample fluid flow, the number of the magnet pair as well as the position of magnet pair are investigated. The optimal parametric condition for complete separation is obtained through the parametric analysis, and the separation principle is further elucidated by the force analysis. The separation of smaller micro and sub-micro diamagnetic particles is finally demonstrated. This study provides an insight into the negative magnetophoretic phenomenon and guides the fabrication of feasible, low-cost diagnostic devices for sub-micro particle separation.     

Atomistic Insight Into the Host–Guest Interaction of a Photoresponsive Metal–Organic Framework

Photoresponsive functional materials have gained increasing attention due to their externally tunable properties. Molecular switches embedded in these materials enable the control of phenomena at the atomic level by light. Metal–organic frameworks (MOFs) provide a versatile platform to immobilize these photoresponsive units within defined molecular environments to optimize the intended functionality. For the application of these photoresponsive MOFs (pho-MOFs), it is crucial to understand the influence of the switching state on the host–guest interaction. Therefore, we present a detailed insight into the impact of molecular switching on the intermolecular interactions. By performing atomistic simulations, we revealed that due to different interactions of the guest molecules with the two isomeric states of an azobenzene-functionalized MOF, both the adsorption sites and the orientation of the molecules within the pores are modulated. By shedding light on the host–guest interaction, our study highlights the unique potential of pho-MOFs to tailor molecular interaction by light.     

Structures,g-tensors,and hyperfine coupling constants of L-α-alanine radicals in radiation dosimetry: An ab initio molecular dynamics simulation study

Alanine is used as a transfer standard dosimeter for gamma ray and electron beam calibration. An important factor affecting its dosimetric response is humidity which can lead to errors in absorbed dose calculations. Ab initio molecular dynamics calculations were performed to determine the environmental effects on the electron paramagnetic resonance (EPR) parameters of L-α-alanine radicals in acidic and alkaline solutions. A new result, not dissimilar to the closed-shell amino acid molecule alanine, is that the non-zwitterionic form of the alanine radical is the stable form in the gas phase while the zwitterionic neutral alanine radical is not a stable structure in the gas phase. Geometric and EPR parameters of radicals in both gas and solution phases are found to be dependent on hydrogen bonding of water molecules with the polar groups and on dynamic solvation. Calculations on the optimized free radicals in the gas phase revealed that for the neutral radical, hydrogen bonding to water molecules drives a decrease in the magnitudes of g-tensor components g _xx and g _yy without affecting neither g _zz component nor the hyperfine coupling constants (HFCCs). The transfer from the gas to solution phase of the alanine radical anion is accompanied with an increase in the spin density on the carboxylic group's oxygen atoms. However, for the neutral radical, this transfer from gas to solution phase is accompanied with the decrease in the spin density on oxygen atoms. Calculated isotropic HFCCs and g-tensor of all radicals are in good agreement with experiment in both acidic and alkaline solutions.     

Alteration in Cross Diffusivities Governs the Nature and Dynamics of Spatiotemporal Pattern Formation

Realizing spatiotemporal patterns out of a chemical reaction diffusion system remains an experimental challenge owing to the difficulty in overcoming the stringent condition of diffusion driven instability. Herein, by considering the spatially extended Gray-Scott model system, we have investigated how the cross diffusivities of the reactants involved influence the nature and dynamics of spatiotemporal patterns. Our study unravels that in absence of diffusion driven instability, spatially inhomogeneous patterns can be obtained for the Gray-Scott model system, and unstable time dependent patterns can be stabilized just by adjusting cross diffusivities of the reactants. Interestingly, the effect of cross diffusion in presence of the diffusion driven instability can differentially alter the speed of pattern formation, and potentially modify the nature of the spatiotemporal patterns obtained under different parametric conditions. Experimental verification of our findings may allow us to observe spatiotemporal patterns beyond the regime of classical Turing instability.     

Theoretical Modeling of the Surface-Guided Self-Assembly of Functional Molecules

Directing the self-assembly of organic building blocks with 2D templates has been a promising method to create molecular superstructures having unique physicochemical properties. In this work the on-surface self-assembly of simple ditopic functional molecules confined inside periodic nanotemplates was modeled by means of the lattice Monte Carlo simulation method. Two types of confinement, that is honeycomb porous networks and parallel grooves of controlled diameter and width were used in the calculations. Additionally, the effect of (pro)chirality of the adsorbing molecules on the outcome of the templated self-assembly was examined. To that end, enantiopure and racemic assemblies were studied and the resulting structures were identified and classified. The obtained findings demonstrated that suitable tuning of the structural parameters of the templates enables directing the self-assembly towards linear and cyclic aggregates with controlled size. Moreover, chiral resolution of the molecular conformers using honeycomb networks with adjusted pore size was found possible. Our theoretical predictions can be helpful in designing structured surfaces to direct self-assembly and polymerization of organic functional building blocks.