Role Of Configurational Entropy Research Articles

Phase stabilized solution combustion processed (Ce0.2La0.2Pr0.2Sm0.2Y0.2)O1.6-δ: An exploration of the dielectric properties

High entropy oxide (HEO) (Ce0.2La0.2Pr0.2Sm0.2Y0.2)O1.6-δ with a phase pure fluorite was synthesized using low-temperature solution combustion. A low-temperature formation of HEO was evidenced at 500 ºC. The HEO formation at 500 ºC was due to the exothermicity of the combustion redox reaction, where the internal temperature might have reached a much higher temperature for a limited amount of time. The presence of Sm2O3 and Y2O3 was visible upto 500 ºC, while La2O3 was detected up to 900 ºC and the HEO fully got stabilized at 1000 ºC with a single-phase, fcc fluorite structure with an Fm-3 m space group. The HEO displays one of its parent oxide Ce-O structural properties as both belong to the fluorite family and had lattice parameters very close to each other. The presence of a secondary phase in the 2 and 3-cation systems and the display of a single phase in the 4 and 5-cation systems indicated the role of configurational entropy in phase stabilization. Raman of HEO also affirmed the formation of HEO at 500 °C, the complete elimination of secondary phases at 1000 °C, and a fully disordered occupancy of various metal cations with severe lattice distortion. A Flake morphology with a nanogranular cluster on the surface was displayed. Dielectric measurements at room temperature showed permittivity (κ) ≈ 29 – 5.7 from 100 Hz to 1 MHz.

Phase Stability in High-Entropy Alloys: The Role of Configurational Entropy

Phase Stability in High-Entropy Alloys: The Role of Configurational Entropy

The Role of Configurational Entropy in Miniprotein Stability.

Predicting protein stability is a challenge due to the many competing thermodynamic effects. Through de novo protein design, one begins with a target structure and searches for a sequence that will fold into it. Previous work by Rocklin et al. introduced a data set of more than 16,000 miniproteins spanning four structural topologies with information on stability. These structures were characterized with a set of 46 structural descriptors, with no explicit inclusion of configurational entropy (Scnf). Our work focused on creating a set of 17 descriptors intended to capture variations in Scnf and its comparison to an extended set of 113 structural and energy model features that extend the Rocklin et al. feature set (R). The Scnf descriptors statistically discriminate between stable and unstable distributions within topologies and best describe EEHEE topology stability (where E = β sheet and H = α helix). Between 50 and 80% of the variation in each Scnf descriptor is described by linear combinations of R features. Despite containing useful information about minipeptide stability, providing Scnf features as inputs to machine learning models does not improve overall performance when predicting protein stability, as the R features sufficiently capture the implicit variations.

Computational property predictions of Ta\u2013Nb\u2013Hf\u2013Zr high-entropy alloys

Refractory high entropy alloys (R-HEAs) are becoming prominent in recent years because of their properties and uses as high strength and high hardness materials for ambient and high temperature, aerospace and nuclear radiation tolerance applications, orthopedic applications etc. The mechanical properties like yield strength and ductility of TaNbHfZr R-HEA depend on the local nanostructure and chemical ordering, which in term depend on the annealing treatment. In this study we have computationally obtained various properties of the equimolar TaNbHfZr alloy like the role of configurational entropy in the thermodynamic property, rate of evolution of nanostructure morphology in thermally annealed systems, dislocation simulation based quantitative prediction of yield strength, nature of dislocation movement through short range clustering (SRC) and qualitative prediction of ductile to brittle transition behavior. The simulation starts with hybrid Monte Carlo/Molecular Dynamics (MC/MD) based nanostructure evolution of an initial random solid solution alloy structure with BCC lattice structure created with principal axes along [1 1 1], [− 1 1 0] and [− 1 − 1 2] directions suitable for simulation of ½[1 1 1] edge dislocations. Thermodynamic properties are calculated from the change in enthalpy and configurational entropy, which in term is calculated by next-neighbor bond counting statistics. The MC/MD evolved structures mimic the annealing treatment at 1800 °C and the output structures are replicated in periodic directions to make larger 384,000 atom structures used for dislocation simulations. Edge dislocations were utilized to obtain and explain for the critically resolved shear stress (CRSS) for the structures with various degrees of nanostructure evolution by annealing, where extra strengthening was observed because of the formations of SRCs. Lastly the MC/MD evolved structures containing dislocations are subjected to a high shear stress beyond CRSS to investigate the stability of the dislocations and the lattice structures to explain the experimentally observed transition from ductile to brittle behavior for the TaNbHfZr R-HEA.

Shallow Iodine Defects Accelerate the Degradation of α-Phase Formamidinium Perovskite

Summary Shallow defects are mostly benign in covalent semiconductors, such as silicon, given that they do not constitute non-radiative recombination sites. In contrast, the existence of shallow defects in ionic perovskite crystals might have significant repercussions on the long-term stability of perovskite solar cells (PSCs) because of the metastability of the ubiquitous formamidinium lead triiodide (FAPbI3) perovskite and the migration of charged point defects. Here, we show that shallow iodine interstitial defects ( I i ) can be generated unintentionally during commonly used post-fabrication treatments, which can lower the cubic-to-hexagonal transformation barrier of FAPbI3-based perovskites to accelerate its phase degradation. We demonstrate that concurrently avoiding the generation of I i and the more effective passivation of iodine vacancies ( V I ) can improve the thermodynamic stability of the films and operational stability of the PSCs. Our most stable PSC retained 92.1 % of its initial performance after nearly 1,000 h of continuous illumination operational stability testing.

Role of configurational entropy in body-centred cubic or face-centred cubic phase formation in high entropy alloys

This study examines the comparative phase stability of transition and late transition element based high entropy alloys in body-centred cubic (BCC) or face-centred cubic (FCC) forms using a combined classical molecular dynamics and statistical mechanics based approach. Multi-configurational sampling was carried out using a hybrid genetic algorithm-molecular dynamics (GA-MD) based method. The calculations demonstrate that comparative BCC or FCC phase stability is influenced by configurational entropy. The present study also provides a theoretical explanation of the recently reported occurrence of BCC phase in CoCrFeNi HEA, where the high temperature structure may be retained.

A novel, single phase, non-equiatomic FeMnNiCoCr high-entropy alloy with exceptional phase stability and tensile ductility

A non-equiatomic FeMnNiCoCr alloy is introduced and characterized at multiple scales employing various characterization techniques (e.g. atom probe tomography, electron channeling contrast imaging, electron backscatter diffraction, etc.) to elucidate (i) the role of configurational entropy and (ii) the intrinsic tensile ductility of high-entropy alloys. Results reveal that the new material is a true high-entropy alloy with a stable random solid solution despite its comparably low configurational entropy, and that it has excellent tensile ductility irrespective of the substantial lattice distortion.

Statistical mechanics and molecular dynamics in evaluating thermodynamic properties of biomolecular recognition

Molecular recognition plays a central role in biochemical processes. Although well studied, understanding the mechanisms of recognition is inherently difficult due to the range of potential interactions, the molecular rearrangement associated with binding, and the time and length scales involved. Computational methods have the potential for not only complementing experiments that have been performed, but also in guiding future ones through their predictive abilities. In this review, we discuss how molecular dynamics (MD) simulations may be used in advancing our understanding of the thermodynamics that drive biomolecular recognition. We begin with a brief review of the statistical mechanics that form a basis for these methods. This is followed by a description of some of the most commonly used methods: thermodynamic pathways employing alchemical transformations and potential of mean force calculations, along with end-point calculations for free energy differences, and harmonic and quasi-harmonic analysis for entropic calculations. Finally, a few of the fundamental findings that have resulted from these methods are discussed, such as the role of configurational entropy and solvent in intermolecular interactions, along with selected results of the model system T4 lysozyme to illustrate potential and current limitations of these methods.

The Role of Configurational Entropy in Amorphous Systems.

Configurational entropy is an important parameter in amorphous systems. It is involved in the thermodynamic considerations, plays an important role in the molecular mobility calculations through its appearance in the Adam-Gibbs equation and provides information on the solubility increase of an amorphous form compared to its crystalline counterpart. This paper presents a calorimetric method which enables the scientist to quickly determine the values for the configurational entropy at any temperature and obtain the maximum of information from these measurements.

Cluster chemistry in the solid state: Structured diffuse scattering, oxide/fluoride ordering and polar behaviour in transition metal oxyfluorides

Oxide/fluoride ordering in three families of ‘disordered’ transition metal oxyfluoride compounds is carefully investigated and used to obtain insight into why the constituent inherently acentric octahedral units do not usually order in a long range ordered polar sense. Observed highly structured diffuse intensity distributions are used in each case to analyze the local crystal chemistry and orientational ordering rules governing the way in which the dipole moments from the individual polar pseudo-octahedral units add together. The common local oxide/fluoride ordering rules, the consequences of these rules for polar behaviour on the local scale as well as the role of configurational entropy and energy minimization in suppressing long range polar order are highlighted.

Role of configurational entropy in the thermodynamics of clusters of point defects in crystalline solids

The internal configurational entropy of point defect clusters in crystalline silicon is studied in detail by analyzing their potential energy landscapes. Both on-lattice and off-lattice calculation approaches are employed to demonstrate the importance of off-lattice configurational states that arise due to a large number of inherent structures (local minima) in the energy landscape generated by the interatomic potential function. The resulting cluster configurational entropy of formation is shown to exhibit behavior that is qualitatively similar to that observed in supercooled liquids and amorphous solids and substantially alters the thermodynamic properties of point defect clusters in crystals at high temperature. This behavior is shown to be independent of interatomic potential and cluster type, and suggests that defects in crystals at high temperature should be generally described by a quasicontinuous collection of nondegenerate states rather than as a single ground state structure. The modified thermodynamic properties of vacancy clusters at high temperature are found to explain a long-standing discrepancy between simulation predictions and experimental measurements of vacancy aggregation dynamics in silicon.

Erratum: “Environmental swap energy and role of configurational entropy in transfer of small molecules from water into alkanes” [J. Chem. Phys. 120, 1383 (2004)

Erratum: “Environmental swap energy and role of configurational entropy in transfer of small molecules from water into alkanes” [J. Chem. Phys. <b>120</b>, 1383 (2004)

Physical and chemical vitrification: the role of configurational entropy

Glasses can be formed in numerous ways, involving very different microscopic processes. Here we report a dielectric and photon-correlation study of chemical vitrification, a process where the slowdown in the dynamics of a liquid system is controlled by the irreversible formation of chemical bonds. We find that vitrification dynamics in chemically reactive systems can be explained in terms of their configurational restrictions in the same manner as in stable glass-forming liquids under cooling or compression.

Environmental swap energy and role of configurational entropy in transfer of small molecules from water into alkanes.

We studied the effect of segmented solvent molecules on the free energy of transfer of small molecules from water into alkanes (hexane, heptane, octane, decane, dodecane, tetradecane, and hexadecane). For these alkanes we measured partition coefficients of benzene, 3-methylindole (3MI), 2,3,4,6-tetrachlorophenol (TeCP), and 2,4,6-tribromophenol (TriBP) at 3, 11, 20, 33 [corrected], and 47 degrees C. For 3MI, TeCP, and TriBP the dependence of free energy of transfer on length of alkane chains was found to be very different from that for benzene. In contrast to benzene, the energy of transfer for 3MI, TeCP, and TriBP was independent of the number of carbons in alkanes. To interpret data, we used the classic Flory-Huggins (FH) theory of concentrated polymer solutions for the alkane phase. For benzene, the measured dependence of energy of transfer on the number of carbons in alkanes agreed well with predictions based on FH model in which the size of alkane segments was obtained from the ratio of molar volumes of alkanes and the solute. We show that for benzene, the energy of transfer can be divided into two components, one called environmental swap energy (ESE), and one representing the contribution of configurational entropy of alkane chains. For 3MI, TeCP, and TriBP the contribution of configurational entropy was not measurable even though the magnitude of the effect predicted from the FH model for short chain alkanes was as much as 20 times greater than experimental uncertainties. From the temperature dependence of ESE we obtained enthalpy and entropy of transfer for benzene, 3MI, TeCP, and TriBP. Experimental results are discussed in terms of a thermodynamic cycle considering creation of cavity, insertion of solute, and activation of solute-medium attractive interactions. Our results suggest that correcting experimental free energy of transfer by Flory-Huggins configurational entropy term is not generally appropriate and cannot be applied indiscriminately.

The role of configurational entropy in biochemical cooperativity.

Cooperativity is a common biochemical phenomenon in which two or more otherwise independent processes are thermodynamically coupled. Because cooperative processes are usually attended by changes in molecular conformation, thermodynamic coupling is usually attributed to an enthalpy-driven mechanism. In the family of glycopeptide antibiotics that includes vancomycin, however, cooperative phenomena occur that cannot be explained by conformational change. In this communication, we demonstrate that cooperativity in these systems can arise solely from changes in vibrational activity.

Overview no. 40 Application of the ANNNI model to long-period superstructures

Existing models of long-period superstructures are re-examined in the light of the recently developed Axial-Next-Nearest-Neighbor-Ising (ANNNI) Model. In this model, long-period phases are contained in a triangular shaped phase diagram region bounded by a Lifshitz point on the uppermost transition temperature line and a multiphase point at zero absolute temperature. Periodic antiphase structures are produced by a square-wave modulation of the ordered ground state, resulting in new types of long-period superstructures, here denoted as “Fujiwara phases.” The role of configurational entropy in stabilizing long-period phases is emphasized. The applicability of the ANNNI model to periodic antiphase structures in ordered alloys is examined, and the striking resemblence between predicted structures and those observed experimentally in Ag 3Mg and Au 3Zn is pointed out. The difference between “straight” and “wavy” (CuAu II) antiphase domain boundaries is discussed in the light of the model.

Molecular Theories of Rubberlike Elasticity and Polymer Viscoelasticity

Abstract The foundation for nearly all the molecular theories of the physical properties of polymers was laid in 1934 when Guth and Mark and Kuhn first recognized the role of configurational entropy of polymer chains. By virtue of ability of their segments to rotate with respect to each other along the chain backbone, macromolecules are capable of assuming a myriad of conformations. It is this long, flexible chain nature of polymer molecules that provides us a link in interpreting the macroscopic physical properties in terms of microscopic molecular dynamics. In this review we shall demonstrate the utilization of conformational statistics in the formulation of molecular theories for two important aspects of the mechanical properties of polymers. The first part deals with the equilibrium elastic response of a crosslinked rubberlike network. A simplified derivation will be given on the basis of the entropic approach. Some of the underlying assumptions will then be examined, and the contribution of internal energy to rubber elasticity scrutinized. The second part describes the transient viscoelastic properties of linear polymers in solution and in bulk. Limitations of the model will be assessed and its applications to experimental data explored. It should be pointed out that a number of reviews are available in the literature both for elasticity and viscoelasticity of polymers. The present work is not an exhaustive review of these fields, but rather concentrates on the more recent developments not previously discussed. The emphasis will be placed upon polymers in the bulk state, although solution properties will be mentioned where appropriate.

MOLECULAR THEORIES OF RUBBER-LIKE ELASTICITY AND POLYMER VISCOELASTICITY

Abstract The foundation for nearly all the molecular theories of the physical properties of polymers was laid in 1934 when Guth and Mark [I], and Kuhn [21 first recognized the role of configurational entropy of polymer chains. By virtue of ability of their segments to rotate with respect to each other along the chain backbone, macromolecules are capable of assuming a myriad of conformations. It is this long, flexible chain nature of polymer molecules that provides us a link in in terpreting the macroscopic physical properties in terms of microscopic molecular dynamics. In this review we shall demonstrate the utilization of conformational statistics in the formulation of molecular theories for two important aspects of the mechanical properties of polymers. The first part deals with the equilibrium elastic response of a cross-linked rubber -like network. A simplified derivation will be given on the basis of the entropic approach. Some of the underlying assumptions will then be examined, and the contribution...