Anisotropic Domains Research Articles

Instability, bifurcation and nonlinear dynamics of Poiseuille flow in fluid overlying an anisotropic and inhomogeneous porous domain

The present study focuses on the finite amplitude analysis of Poiseuille flow in an anisotropic and inhomogeneous porous domain that underlies a fluid domain. The nonlinear interactions are studied by imposing finite amplitude disturbances to the Poiseuille flow. The former interactions in terms of modal amplitudes dictate the fundamental mode, the distorted mean flow, the second harmonic and the distorted fundamental mode. The harmonics are solved progressively in increasing order of the least stable mode obtained from the linear theory to ascertain the cubic Landau equation, which in turn helps to determine the bifurcation phenomena. The presented weakly nonlinear theory predicts the existence of subcritical transition to turbulence of Poiseuille flow in such superposed systems. In general, on moving away from the bifurcation point, it is found that a decrease in the value of inhomogeneity (in terms of Ai), Darcy number (δ) and an increase in the value of depth ratio (dˆ; the ratio of fluid domain thickness to that of porous domain) favours subcritical bifurcation. For the considered variation of parameters, the bifurcation, either subcritical or supercritical, remains the same irrespective of the value of media anisotropy (ξ) in the vicinity of the bifurcation point except for dˆ=0.2,Ai=1. In such a situation, subcritical (supercritical) bifurcation is witnessed for ξ=0.001,0.01,0.1 (1,3). Furthermore, in contrast to isotropic and homogeneous porous media, both subcritical and supercritical bifurcations are observed when moving away from the bifurcation point. A correspondence between the type of mode via linear theory and the type of bifurcation via nonlinear theory is witnessed, which is further affirmed by the secondary flow patterns. Finally, the presented theoretical results reveal an early onset of subcritical transition to turbulence in comparison with isotropic and homogeneous porous media.

Coupled Electrochemical-Thermal Runaway Model of Lithium-Ion Cells Operating Under High Ambient Temperatures

The risk of thermal runaway (TR) in high energy density Lithium-ion batteries (LIBs), which may initiate at around 90 °C, is a critical safety concern, particularly in regions where summer temperatures can reach nearly 50 °C. While multiple exothermic reactions that cause TR and modeled using Arrhenius equations lead to good predictions in controlled oven tests, their use in practical applications is questionable as these do not consider internal electrochemical processes that cause temperature rise and trigger exothermic reactions. Further, limited literature focuses on coupling electrochemical thermal models with exothermic reactions. This study demonstrates a method to couple the electrochemical and thermal runaway models for a commercial cylindrical Lithium-ion cell. The proposed model averages pseudo-2D electrochemical heat and couples it to a two-dimensional, axisymmetric heat transfer model of 18650-type Lithium-ion cell. The jellyroll structure is approximated as a homogeneous and anisotropic domain for electrochemical and exothermic heating. Simulations are performed through several, uninterrupted charge-discharge cycles at different ambient temperatures and C-rates. We show that while cycling rate is critical in instigating and accelerating TR, parameters like ambient temperature, particle radii and initial electrolyte concentration also play a role in determining the core temperature and its rate of growth in the cell.

Patchwork structure of continental lithosphere captured in 3D body wave images of its anisotropic fabrics

This paper presents an overview of research conducted for more than five decades around Vladislav Babuška and collaborators on large-scale seismic anisotropy in tectonically different regions of continental lithosphere in Europe. A wide range of independent data sets and methods are covered. It also briefly touches laboratory measurements of velocity anisotropy on rock samples from the crust and the upper mantle, and emphasizes the importance of considering anisotropy in studies of the Earth structure. The anisotropy is responsible for even larger velocity variations than those due to composition of the most abundant upper mantle rocks (peridotites). The large-scale in-situ measurements of the upper mantle anisotropy capture fabrics of the mantle lithosphere, and enables mapping lateral changes in its structure. The joint inversion/interpretation of the teleseismic body-wave anisotropic parameters, such as variations of directional terms of relative travel time residuals of P waves, shear-wave splitting or the coupled anisotropic-isotropic teleseismic P-wave tomography, image the continental lithosphere as a mosaic of anisotropic domains. Each of the domains has its own thickness and fossil fabric characterized by tilted symmetry axes. We map boundaries of the domains in dependence on the fabric changes. The boundaries can be either narrow and steep or broader and inclined, with an offset relative to boundaries of the related crustal bocks, which can reach several tens of kilometres. This overview presents the European lithosphere-asthenosphere boundary (LAB) and shows examples of anisotropic fabrics of the mantle lithosphere domains and their boundaries in different parts of the European plate.

Insight into the Evolution of the Eastern Margin of the Wyoming Craton from Complex, Laterally Variable Shear Wave Splitting

Abstract Dense seismic arrays such as EarthScope’s Transportable Array (TA) have enabled high-resolution seismic observations that show the structure of cratonic lithosphere is more heterogeneous and complex than previously assumed. In this study, we pair TA data with data from the Bighorn Arch Seismic Experiment and the Crust and lithosphere Investigation of the Easternmost expression of the Laramide Orogeny (CIELO) to provide unprecedented detail on the seismic anisotropic structure of the eastern margin of the Wyoming Craton, where several orogens emerged from nominally strong cratonic lithosphere during the Laramide Orogeny. In this study, we use the splitting of teleseismic shear waves to characterize fabrics associated with deformation in the Earth’s crust and mantle. We constrain distinct anisotropic domains in the study area, and forward modeling shows that each of these domains can be explained by a single layer of anisotropy. Most significantly, we find a fast direction in the southern part of the Powder River Basin, which we refer to as the Thunder Basin Block (TBB), that deviates from absolute plate motion (APM). This change in splitting behavior coincides with changes in other modeled geophysical observations, such as active source P-wave velocity models, potential field modeling, and seismic attenuation analysis, which all show a significant change moving from the Bighorn Mountains to the TBB. We argue that these results correspond to structure predating the Laramide Orogeny, and most likely indicate a Neoarchean boundary preserved within the lithosphere.

3D Ferroelectric Phase Field Simulations of Polycrystalline Multi‐Phase Hafnia and Zirconia Based Ultra‐Thin Films

AbstractHfO2– and ZrO2–based ferroelectric thin films have emerged as promising candidates for the gate oxides of next‐generation electronic devices. Recent work has experimentally demonstrated that a tetragonal/orthorhombic (t/o‐) phase mixture with partially in‐plane polarization can lead to negative capacitance (NC) stabilization. However, there is a discrepancy between experiments and the theoretical understanding of domain formation and domain wall motion in these multi‐phase, polycrystalline materials. Furthermore, the effect of anisotropic domain wall coupling on NC has not been studied so far. Here, 3D phase field simulations of HfO2– and ZrO2–based mixed‐phase ultra‐thin films on silicon are applied to understand the necessary and beneficial conditions for NC stabilization. It is found that smaller ferroelectric grains and a larger angle of the polar axis with respect to the out‐of‐plane direction enhances the NC effect. Furthermore, it is shown that theoretically predicted negative domain wall coupling even along only one axis prevents NC stabilization. Therefore, it is concluded that topological domain walls play a critical role in experimentally observed NC phenomena in HfO2– and ZrO2–based ferroelectrics.

Extending Finch-Skea isotropic model to anisotropic domain in modified f(, T ) gravity

This paper considers the Finch-Skea isotropic solution and extends its domain to three different anisotropic interiors by using the gravitational decoupling strategy in the context of f(R,T) gravitational theory. For this, we consider that a static spherical spacetime is initially coupled with the perfect matter distribution. We then introduce a Lagrangian corresponding to a new gravitating source by keeping in mind that this new source produces the effect of pressure anisotropy in the parent fluid source. After calculating the field equations for the total matter setup, we apply a transformation on the radial component, ultimately providing two different systems of equations. These two sets are solved independently through different constraints that lead to some new solutions. Further, we consider an exterior spacetime to calculate three constants engaged in the seed Finch-Skea solution at the spherical interface. The estimated radius and mass of a star candidate LMC X-4 are utilized to perform the graphical analysis of the developed models. It is concluded that only the first two resulting models are physically relevant in this modified theory for all the considered parametric choices.

Elucidating Structural Disorder in Ultra-Thin Bi-Rich Bismuth Oxyhalide Photocatalysts.

Advancing the field of photocatalysis requires the elucidation of structural properties that underpin the photocatalytic properties of promising materials. The focus of the present study is layered, Bi-rich bismuth oxyhalides, which are widely studied for photocatalytic applications yet poorly structurally understood, due to high levels of disorder, nano-sized domains, and the large number of structurally similar compounds. By connecting insights from multiple scattering techniques, utilizing electron-, X-ray- and neutron probes, the crystal phase of the synthesized materials is allocated as layered Bi24O31X10 (X = Cl, Br), albeit with significant deviation from the reported 3Dcrystalline model. The materials comprise anisotropic platelet-shaped crystalline domains, exhibiting significant in-plane ordering in two dimensionsbut disorder and an ultra-thin morphology in the layer stacking direction. Increased synthesis pH tailored larger, more ordered crystalline domains, leading to longer excited state lifetimes determined via femtosecond transient absorption spectroscopy (fs-TAS). Although this likely contributes to improved photocatalytic properties, assessed via the photooxidation of benzylamine, increasing the overall surface area facilitated the most significant improvement in photocatalytic performance. This study, therefore, enabled both phase allocation and a nuanced discussion of the structure-property relationship for complicated, ultra-thin photocatalysts.

Solid bitumen as an indicator of petroleum migration, thermal maturity, and contact metamorphism: A case study in the Barrandian Basin (Silurian - Devonian), Czech Republic

Silurian and Devonian marine shales and limestones of the Barrandian Basin host abundant black solid, non-fluorescing bitumens that fill tectonic fractures and veins, and occlude fossil moulds and diagenetic concretions. Solid bitumen, interpreted as thermally degraded petroleum, entered the rocks during several successive episodes of fracture-bound petroleum migration that occurred during deeper burial of the strata. Regional distribution of bitumen reflectance values that range between ∼0.9–2.3% Rr, correlate with variations of its FT-IR and Raman spectroscopic characteristics and aromatic hydrocarbon composition, and collectively evidence the maturity trend increasing across the basin from the southwest to the northeast. The reflectance of chitinozoans and graptolites (∼0.8–1.9% Rr) in the country rocks and homogenization temperatures of hydrocarbon fluid inclusions document palaeotemperatures ranging between ∼90–150 °C, characteristic of the oil window zone grading into the gas/condensate zone. Although in a basin-wide perspective the averaged values of solid bitumen and zooclast optical reflectance converge and indicate the same northeastern-increasing regional diagenetic trend, solid bitumen reflectance values vary considerably at individual localities and even within some bitumen samples. The wide scatter of optical reflectance values and the heterogeneity of optical properties, which were attributed to the presence of multiple source rocks in the basin, the variable lithology of bitumen host rocks, or other variables, hamper the use of solid bitumen as a simple alternative to zooclast/vitrinite reflectance palaeothermometers in a given basin. On the other hand, the highly anisotropic domain and the mesophase “coking” textures of the solid bitumen that were recognized in the NE part of the basin provide unique evidence on an anomalous, hitherto unrecognized, geologically short-lasting thermal event that affected the Palaeozoic rocks. A line of indirect evidence suggests that the coking of the bitumen was caused by a cryptic intrusion, possibly a concealed branch of the Central Bohemian Pluton, which intruded into the strata during the Variscan orogeny. More rarely occurring semi-solid, vividly yellow fluorescing waxy bitumen, that postdates solid bitumen in some fractures and voids, does not reveal a regional thermal maturation trend. It precipitated from relict waxy oils that migrated through the strata during a post-Neogene uplift of the Barrandian region.

The intrinsic switching field of single domain ferromagnetic particles

The intrinsic switching field defined as the minimum field to induce spontaneous magnetic reversal is calculated at finite temperatures for a uniaxially anisotropic single domain particle using a formalism based on the generalized free energy function of the system. For a fine ferromagnetic particle coupled to a constant temperature heat bath, the switching field is smaller than the field predicted by the Stoner-Wohlfarth (SW) theory and the difference is dependent on the direction of the applied field resulting in breaking of the symmetry of the SW astroid.

Impact of Temperature on the Chiroptical Properties of Thin Films of Chiral Thiophene-based Oligomers.

According to the theoretical model based on the Mueller matrix approach, the experimental electronic circular dichroism (ECD) for thin films of chiral organic dyes can be expressed as the sum of several contributions, two of which are the most significant: 1) an intrinsic component (CDiso) invariant upon sample orientation, reflecting the molecular and/or supramolecular chirality, due to 3D-chiral nanoscopic structures; 2) a non-reciprocal component (LDLB) which inverts its sign upon sample flipping, which arises from the interaction of linear dichroism and linear birefringence in locally anisotropic domains, expression of 2D-chiral micro/mesoscopic structures. In this work, we followed in parallel through ECD and differential scanning calorimetry (DSC) the temperature evolution of the supramolecular arrangements of thin films of five structurally related chiral thiophene-based oligomers with different LDLB/CDiso ratio. By increasing the temperature, regardless of phase transitions observed by DSC analysis, systems with strong CDiso revealed no changes in the ECD spectrum, while compounds with dominant LDLB contribution underwent a gradual (and reversible) reduction of (apparent) ECD signals. These findings demonstrated that the concomitant occurrence of intrinsic and non-reciprocal components in the ECD spectrum of thin films of chiral organic dyes is strictly correlated with solid-state organizations of different stability.

Sharp estimates for the first Robin eigenvalue of nonlinear elliptic operators

The aim of this paper is to obtain optimal estimates for the first Robin eigenvalue of the anisotropic p-Laplace operator, namely:λ1(β,Ω)=minψ∈W1,p(Ω)∖{0}⁡∫ΩF(∇ψ)pdx+β∫∂Ω|ψ|pF(νΩ)dHN−1∫Ω|ψ|pdx, where p∈]1,+∞[, Ω is a bounded, anisotropic mean convex domain in RN, νΩ is its Euclidean outward normal, β is a real number, and F is a sufficiently smooth norm on RN. The estimates we found are in terms of the first eigenvalue of a one-dimensional nonlinear problem, which depends on β and on geometrical quantities associated to Ω. More precisely, we prove a lower bound of λ1 in the case β>0, and a upper bound in the case β<0. As a consequence, we prove, for β>0, a lower bound for λ1(β,Ω) in terms of the anisotropic inradius of Ω and, for β<0, an upper bound of λ1(β,Ω) in terms of β.

Universal Stripe Symmetry of Short-Range Charge Density Waves in Cuprate Superconductors.

The omnipresence of charge density waves (CDWs) across almost all cuprate families underpins a common organizing principle. However, a longstanding debate of whether its spatial symmetry is stripe or checkerboard remains unresolved. While CDWs in lanthanum- and yttrium-based cuprates possess a stripe symmetry, distinguishing these two scenarios is challenging for the short-range CDW in bismuth-based cuprates. Here, high-resolution resonant inelastic x-ray scattering is employed to uncover the spatial symmetry of the CDW in Bi2 Sr2 - x Lax CuO6 + δ . Across a wide range of doping and temperature, anisotropic CDW peaks with elliptical shapes are found in reciprocal space. Based on Fourier transform analysis of real-space models, the results are interpreted as evidence of unidirectional charge stripes, hosted by mutually 90°-rotated anisotropic domains. This work paves the way for a unified symmetry and microscopic description of CDW order incuprates.

Effects of drawing and tension stress annealing on the structure and magnetic properties of Co-based amorphous wire

Cold drawing significantly improves the size uniformity of the amorphous wire, but leads to wire curling. Tensile stress annealing (TSA) is the key to regulating the straightness and magnetic properties of Co-based amorphous wires, but their intrinsic correlation is still unclear. Herein, the effects of TSA on the morphology, microstructure, soft magnetic properties and longitudinal driven giant magneto-impedance (LD-GMI) effect of cold drawn Co-based amorphous wires have been studied in detail. It was found that increasing tensile stress can effectively straighten the drawn amorphous wire, yet at the cost of decreasing fracture strength, increasing coercivity and deteriorating GMI effect. Furthermore, appropriate annealing can restore the magnetic properties of the TSA amorphous wire. The variation of magnetic properties is relative to the change of circular anisotropic field and magnetic domain structure.

Charged anisotropic compact stellar models under gravitational decoupling scheme

The aim of this paper is to obtain new physically admissible exact anisotropic stellar models via gravitational decoupling technique. This will be done by taking Korkina and Orlyanskii model solution as a seed solution and extend it to an anisotropic domain via gravitational decoupling through the minimal geometric deformation (MGD) approach. We analyze the physical properties of four compact star models Her [Formula: see text] (Mass [Formula: see text], [Formula: see text][Formula: see text]km), LMC [Formula: see text] ([Formula: see text], [Formula: see text][Formula: see text]km), PSR [Formula: see text] ([Formula: see text], [Formula: see text][Formula: see text]km) and PSR [Formula: see text] ([Formula: see text], [Formula: see text][Formula: see text]km). We demonstrate the stability conditions of the obtained solution by plotting energy conditions, velocity of sound, adiabatic index and all the thermodynamic parameters and equilibrium conditions via TOV equation, etc. We found that the results are physically well behaved and also fulfill the requirement of stability criteria inside the anisotropic fluid sphere. We study the physical features of the solutions in detail, analytically and graphically for the four compact stars Her [Formula: see text], LMC [Formula: see text], PSR [Formula: see text] and PSR [Formula: see text]. Based on the results we realized that the extended gravitational decoupling technique is very effective for the analysis of the interior of the compact stellar structures.

A Study of Free-Form Shape Rationalization Using Biomimicry as Inspiration.

Bridging the gap between the material and geometrical aspects of a structure is critical in lightweight construction. Throughout the history of structural development, shape rationalization has been of prime focus for designers and architects, with biological forms being a major source of inspiration. In this work, an attempt is made to integrate different phases of design, construction, and fabrication under a single framework of parametric modeling with the help of visual programming. The idea is to offer a novel free-form shape rationalization process that can be realized with unidirectional materials. Taking inspiration from the growth of a plant, we established a relationship between form and force, which can be translated into different shapes using mathematical operators. Different prototypes of generated shapes were constructed using a combination of existing manufacturing processes to test the validity of the concept in both isotropic and anisotropic material domains. Moreover, for each material/manufacturing combination, generated geometrical shapes were compared with other equivalent and more conventional geometrical constructions, with compressive load-test results being the qualitative measure for each use case. Eventually, a 6-axis robot emulator was integrated with the setup, and corresponding adjustments were made such that a true free-form geometry could be visualized in a 3D space, thus closing the loop of digital fabrication.

Site-selective growth and plasmonic spectral properties of L-shaped Janus Au-Ag gold nanodumbbells for surface-enhanced Raman scattering

Ligand-mediated interface control has been broadly applied as a powerful tool in constructing asymmetric multicomponent nanoparticles (AMNP), and induces the anisotropic growth with fine-tuning morphology, composition, plasmonic property and functionality. As a new kind of AMNP, the synthesis of Janus Au-Ag nanoparticles with tunable negative surface curvature is still a challenge. Here, we demonstrate that the synergistic surface energy effects between gold nanodumbbells (Au NDs) with a negative surface curvature and 4-mercaptobenzoic acid (4-MBA) can direct the site-selective growth of anisotropic silver domains on gold nanodumbbells (Au NDs@Ag NPs). By adjusting the 4-MBA concentration-dependent interfacial energy, the Au NDs@Ag NPs could be continuously tuned from dumbbell-like core–shell structures, to L-shaped Janus, and then rod-like core–shell structures with directional and asymmetric spatial distributions of resizable Ag domains by site-selective growth. Based on the calculation results of discrete dipole approximation (DDA) method, it has been found that the Au NDs@Ag L-shaped Janus NPs with Ag island domains created polarization orientation-dependent plasmonic extinction spectra and hot spots around the negatively curved waist and Ag domains. The L-shaped Janus Au NDs@Ag NPs exhibited significantly plasmonic spectrum properties with four apparent LSPR peaks that cover from visible to near-infrared range and higher surface-enhanced Raman scattering (SERS) activity compared with the original Au NDs. The best SERS enhancement factor of 1.41 × 107 was achieved. This synergistic surface energy effect-based method involving the asymmetric growth of silver coating on gold nanoparticles with negatively curved surface presents a new method to design and fabricate nanometer optical devices based on asymmetric multicomponent nanoparticles.

The influence of calcium formate on the hydration of calcium sulfate hemihydrate

In this study, the influence of calcium formate (CF) on the hydration of a synthesized calcium sulfate hemihydrate (HH) powder was investigated. Isothermal calorimetry measurements showed that CF retards the hydration reaction of HH. This was confirmed by XRD of stored samples and pore solution analysis. Two retardation mechanisms were identified. The combination of pore solution and laser granulometric experiments revealed that firstly, the initial dissolution of hemihydrate decelerates because of high Ca2+ ion concentrations, donated by the faster dissolving CF. Secondly, the HCOO− species of CF adsorb on surfaces of the gypsum crystals, as further pore solution measurements showed. This impedes their formation kinetic. The gypsum crystals exhibited anisotropic peak narrowing in XRD measurements when CF was added. This was caused by a morphology change, which could be verified using the anisotropic domain size morphology approach during Rietveld refinement analysis and SEM images. Gypsum crystals exhibit a blockier shape with CF addition compared to the usual acicular shape in pure water.

Complexity-free solution generated by gravitational decoupling for anisotropic self-gravitating star in symmetric teleparallel f(Q)-gravity theory

In this work, we attempt to find an anisotropic solution for a compact star generated by gravitational decoupling in f(Q)-gravity theory having a null complexity factor. To do this, we initially derive the complexity factor condition in f(Q) gravity theory using the definition given by Herrera (Phys Rev D 97:044010, 2018) and then derived a bridge equation between gravitational potentials by assuming complexity factor to be zero (Contreras and Stuchlik in Eur Phys J C 82:706, 2022). Next, we obtain two systems of equations using the complete geometric deformation (CGD) approach. The first system of equations is assumed to be an isotropic system in f(Q)-gravity whose isotropic condition is similar to GR while the second system is dependent on deformation functions. The solution of the first system is obtained by Buchdahl’s spacetime geometry while the governing equations for the second system are solved through the mimic constraint approach along with vanishing complexity condition. The novelty of our work is to generalize the perfect fluid solution into an anisotropic domain in f(Q)-gravity theory with zero complexity for the first time. We present the solution’s analysis to test its physical viability. We exhibit that the existence of pressure anisotropy due to gravitational within the self-gravitating bounded object plays a vital role to stabilize the f(Q) gravity system. In addition, we show that the constant involved in the solution controls the direction of energy flow between the perfect fluid and generic fluid matter distributions.

Stacking domain morphology in epitaxial graphene on silicon carbide

Terrace-sized, single-orientation graphene can be grown on top of a carbon buffer layer on silicon carbide by thermal decomposition. Despite its homogeneous appearance, a surprisingly large variation in electron transport properties is observed. Here, we employ Aberration-Corrected Low-Energy Electron Microscopy (AC-LEEM) to study a possible cause of this variability. We characterize the morphology of stacking domains between the graphene and the buffer layer of high-quality samples. Similar to the case of twisted bilayer graphene, the lattice mismatch between the graphene layer and the buffer layer at the growth temperature causes a moir\'e pattern with domain boundaries between AB and BA stackings. We analyze this moir\'e pattern to characterize the relative strain and to count the number of edge dislocations. Furthermore, we show that epitaxial graphene on silicon carbide is close to a phase transition, causing intrinsic disorder in the form of co-existence of anisotropic stripe domains and isotropic trigonal domains. Using adaptive geometric phase analysis, we determine the precise relative strain variation caused by these domains. We observe that the step edges of the SiC substrate influence the orientation of the domains and we discuss which aspects of the growth process influence these effects by comparing samples from different sources.

Preparation of mesophase pitch with domain textures by molecular regulation of ethylene tar pitch for boosting the performance of its carbon materials

The fast formation of mosaic optical textures is one of main factors limited its application in high performance carbon materials due to active components containing olefins in ethylene tar pitch (ETP). In this paper, a thermal pretreatment process is proposed for effective molecular reformation of ETP, especially for separation of these active components containing olefins. Mesophase pitch with developed rheological properties and domain anisotropic textures was then prepared via polymerization of the post-treated ETP. Molecular structures analysis results show that these active components containing olefins in ETP prefer to form macromolecules consisted of multiple aromatic cores via rapid radical reactions, and develop a mixed anisotropic texture consequently. Nevertheless, these normal aromatic components tend to produce a semi-rigid molecular structure with less aromatic cores by aliphatic chains transfer reactions and stable radical polymerization reactions. This architecture facilitates its molecular stacking and orientation thus the prepared mesophase pitch (ETP-MP) shows better anisotropic domain texture. The prepared mesophase pitch had suitable performance for the application in needle cokes and carbon foams. This work will help to expand the manufacturing of ETP-derived carbon materials through molecular reformation.