Formation Of State Research Articles

Delta-shocks and vacuums in Riemann solutions to the Umami Chaplygin Aw–Rascle model

This paper is concerned with the formation of delta-shocks and vacuum states for zero-pressure Euler equations. With the introduction of the Umami Chaplygin gas, the Riemann problem for Aw–Rascle model with the reasonable flux-function is solved analytically. The three kinds of Riemann solutions involving the delta-shock are obtained. The generalized Rankine–Hugoniot relation and entropy condition for delta-shock are clarified. Under the entropy condition, the existence and uniqueness of the delta-shock solution are established by solving the generalized Rankine–Hugoniot relation. It is rigorously shown that as the Umami Chaplygin gas pressure and flux-function approach to zero simultaneously, the Riemann solutions of the considered model converge to these of the zero-pressure Euler equations. The numerical results support the theoretical analysis in the end.

Influence of local structure and metal-oxygen hybridization on the electrical and magnetic properties of alkaline earth metal (Mg2+, Ca2+, Sr2+) substituted LaFeO3 ceramics

Pristine and alkaline-earth metal-substituted LaFeO3 (La1−xAxFeO3−δ; x = 0 and 0.2; A = Mg2+, Ca2+, and Sr2+) sintered ceramics are prepared from nanoparticles synthesized via a low-temperature citrate sol–gel technique. X-ray diffraction studies confirm the formation of a phase-pure LaFeO3 structure without any secondary phases for all the La1−xAxFeO3−δ compositions. LaFeO3 and La0.8Mg0.2FeO3−δ ceramics show Raman active modes related to La vibration, oxygen octahedral tilting, bending, and stretching. The optical bandgap is estimated to be 2.34 eV for pure LaFeO3 and reduces to 2.23 eV for La0.8Mg0.2FeO3−δ ceramics. On the contrary, La0.8Ca0.2FeO3−δ and La0.8Sr0.2FeO3−δ ceramics show no features in Raman spectra, consistent with the observation of metallic nature and diffuse band edge without any indication of sharp band edge noted. X-ray absorption spectroscopy (XAS) studies on La-L3 and Fe-K-edges confirm the oxidation states of La3+ and Fe3+ in all these ceramics. Local structural distortions and formation of oxygen vacancies in La0.8A0.2FeO3−δ (A = Mg2+, Ca2+, and Sr2+) ceramics are discerned from XAS structure analysis compared to the pristine LaFeO3 ceramics. Magnetic measurements of La1−xAxFeO3−δ reveal weak ferromagnetic nature except for La0.8Mg0.2FeO3−δ, which shows a large magnetization of 4.6 (6.7) emu/g at 300 (5) K. The ferromagnetic behavior of La0.8Mg0.2FeO3−δ ceramics seems to originate from the modification of hybridization between Fe(3d)–O(2p), La(5d)–O(2p), and Fe(4sp)–O(2p) orbitals. An anomalous magnetic transition observed only in zero-field-cooled curves at 88 K in La0.8Ca0.2FeO3−δ and La0.8Sr0.2FeO3−δ ceramics is correlated to the formation of new electronic states containing O 2p character as discerned from pre-peak O-K-edge.

Crucial Role of the Heteroatom and Bite Angle Influencing Spin States and Dinuclear Fe(II) Helicate Formation in 1,3,4-Thia/Oxadiazole Ligand

Crucial Role of the Heteroatom and Bite Angle Influencing Spin States and Dinuclear Fe(II) Helicate Formation in 1,3,4-Thia/Oxadiazole Ligand

Tube-like Gold Clusters M2@Au17 q (M = W, Mo; q = 0, ±1): Structure, Electronic Property, and Optical Nonlinearity.

Density functional theory (DFT) calculations are carried out to determine the geometries and electronic and nonlinear optical (NLO) properties of the doubly doped gold clusters in three charge states M2 @ Au17 q with M = W, Mo and q = 0, ±1. At their lowest-lying equilibrium structures, the impurities that are vertically encapsulated inside a cylindrical gold framework, significantly enhance the stability and modify properties of the host. The presence of M2 units results in the formation of a tube-like ground state, which is identified for the first time for gold clusters. Having 30 itinerant electrons, the electron shell of M2@Au17 - can be described as 1S21P61D102S2{1F xz 2 21F yz 2 2}1F z 3 2{1F xyz 21F z(x 2-y 2) 2}{1F y(3x 2 -y 2),1F x(x 2 -3y 2)}. The species is thus stabilized upon doping, but it is not a magic cluster. The optical transitions are shifted to the lower-energy region upon doping Mo and W atoms into Au17 q . The static and dynamic NLO properties of M2@Au17 q are also computed and compared to those of the pure Au19 q (having the same number of atoms) and an external reference molecule, i.e., para-nitroaniline (p-NA). For hyperpolarizabilities, the doped clusters possess smaller values than those of their pure counterparts but much larger values than the p-NA. Of the doubly doped systems, the neutral M2@Au17 exhibits particularly high first and second hyperpolarizability tensors. The doped cluster units can also be used as building blocks for the design of gold-based nanowires with outstanding electronic and optical characteristics.

Digital twins’ kinetics of virtual free-radical copolymerization of vinyl monomers with stable radicals. 1. Methyl methacrylate

The first experience of virtual free-radical polymerization of a set of vinyl monomers within the framework of the digital twins (DTs) concept (Polymers 2023, 15, 2999) is extended to methyl methacrylate, copolymerized with small additives of stable radicals such as fullerene C60 and TEMPO. A set of elementary reactions, covering the initial stage of the polymerization, is considered. The calculations, encompassing about 30 DTs, were carried out using a semi-empirical version of the unrestricted two-determinant Hartree-Fock approximation. The main energy and spin-density parameters of the ground state of DTs are determined. The barrier profiles of the decomposition of three DTs were calculated laying the foundation for determining the activation energy of the studied processes. The decisive role of spins in the formation of transition states is confirmed. A drastic difference in the copolymerization with fullerene C60 and TEMPO is established. The obtained virtual kinetic data are in a full consent with experimental reality.

Harnessing Solar Power for Oxidation of Organic Compounds by Re(I)Dipyrrinato Complexes.

Metal dipyrrinato complexes of 4d and 5d metals have distinctive features such as high absorption coefficients in the visible section and room temperature phosphorescence in the red region. This work demonstrates the light-assisted oxidation of organic compounds employing rhenium(I)dipyrrinato complexes as catalysts. The heavy atom effect in rhenium(I)dipyrrinato complexes leads to the formation of long-lived triplet excited states, and these complexes can generate singlet oxygen in excellent yields (up to 84 %). A method was developed for photocatalytic aerobic oxidation of sulfides and amines using only 0.05 mol % and 0.025 mol % of the rhenium(I)dipyrrinato complexes, respectively. The method is efficient, and within 2 h, a variety of substrates were oxidized to produce sulfoxides and imines in high yields (up to 97 %). Rhenium(I)dipyrrinato complexes work very well both in visible light and sunlight, making them promising candidates for photocatalytic applications.

State Formation and Bureaucratization: Evidence from Pre-Imperial China

This paper studies the relationship between military conflicts and state-building in pre-imperial China. I develop an incomplete contract model to examine rulers’ and local administrators’ incentives in conflict. Defensive wars drive decentralization: landowning local administrators have more to gain from a successful defense and are therefore more committed to it. Offensive wars drive centralization: the landowning ruler has personnel control over the non-land-owning local administrator and can therefore force the latter to participate in less lucrative attacks. Model predictions are corroborated with empirical evidence and historical case studies, and offer broader implications for the political divergence between China and Europe.

DFT modeling of reaction of H2 with O2 pre-adsorbed on In2O3(011) surface

The DFT approach is used for the first time to model the reaction of hydrogen with oxygen molecule adsorbed on the defective surface of In2O3(011). This reaction is crucial for hydrogen detection by In2O3 sensor. The activation energies are calculated using two mechanisms involving the formation of both an adsorbed water molecule and hydroxyl groups on the In2O3(011) surface. One hydroxyl group is formed due to the bonding of OH with the surface metal atom, and the other due to the bonding of hydrogen with oxygen of the lattice. Both reactions are characterized by the presence of a potential barrier and are exothermic. The activation energies of the two reactions are calculated by the climbing-image nudged elastic band method to be 0.99 eV and 0.98 eV. The results of the calculations are compared with available experimental data. It is also shown that the presence of a surface neutral oxygen vacancy leads to the formation of a vacancy state below the Fermi level, and the electron density is concentrated on the fourfold coordinated indium atom.

Ūzūn Ḥasan and Timurid Legitimacy

Some of the Turkmen polities that arose in the wake of the waning Chinggisid power in Western Asia sought legitimation by emphasizing their connections with the myths and traditions of Oghuz Khan, perhaps in emulation of the powerful ascriptive claims of the Chinggisid Golden Family (Altan Urūgh) itself. This was particularly true of such groupings (ulūs) as the Qarāquyūnlū and Āqquyūnlū. The latter, the Āqquyūnlū, framed an elaborate genealogy in which they claimed to belong to the lineage of Bāyandur Khan, who was, according to some historians, a grandson of Oghuz Khan and whose descendants were distinguished by specific designs or brands (tamghā). The Āqquyūnlū or Bāyanduriya rulers utilized these designs on coinage, documents, architectural monuments, and banners in appealing to these Oghuz traditions. In doing so, they seemed to have been primarily concerned with competition with their Turkmen rivals. Figure 1 shows the use of the Bāyandur tamghā on a coin of Ūzūn Ḥasan’s Grandfather Qarā ʿUsmān (ruled 780-839/1378-1435); Figure 2, the heading of a document issued by the chancellery of Ūzūn Ḥasan and dated 876/1471.The rise of Tīmūr and the evolution of the Timurid polity in Transoxiana and Khurasan had a significant impact not only on the balance of military and political power throughout Western Asia and the Caucasus region, but also exerted a strong influence on the manner in which later state formations fashioned structures of political legitimacy. Some of these notions, while not originating with Tīmūr and his successors, nevertheless gained great importance as a result of Tīmūr’s conquests and his legacy as it took shape under his son Shāhrukh. As noted by Christopher Markiewicz in the quotation at the beginning of this essay, Ṣāḥib-Qirān and Mujaddidare two of the most important concepts that became increasingly common in the political and religio-political discourse of the ninth-tenth/fifteenth-sixteenth centuries. Both terms will now be discussed in connection with the career of Ūzūn Ḥasan Bāyandur.

‘달리뜨스탄(Dalitstan)’: 인도 식민지 말기 달리뜨 분리주의의 맥락과 성격

History of Modern India witnessed the struggles and negotiations of Dalits, the former Untouchables to secure their rights in various fields. Their movement, with its various stages from collective awakening to political entitlement, and to new cultural identity making, has primarily been led by B. R. Ambedkar. All these activities of Dalit movement have persisted amidst political upheaval of national movement and state formation in India. Dalits, facing the late-colonial and early republican circumstances, had to construct their own identity which survived the ‘all-embracing’ Hindu identity and to secure the safeguards as a minority while being recognized as the equal citizens of Republic of India. This research pays attention to the separatism of Dalit community suggested by Ambedkar during the 1940s and onwards. In the political process of the 1930s, he established a separate Dalit party and demanded separate electorates to become a political entity separate from Hindus, which was not fulfilled as his original demand. During the state-formation period of 1940s, separatist ideas have been presented by various minority groups. Ambedkar suggested his idea on geographical separatism for Dalits. The demand for separate settlements was proposed along with the political entity separated from Hindus through separate electorates, appropriate representation in public offices and budgets. Unlike the separatism of religious minority groups, Dalit separatism was not aimed at establishing an independent nation-state but was a practical alternative to overcome the poor economic base of Dalits and escape caste Hindu discrimination in villages. Dalitstan had the meaning of a liberated zone for Dalits without caste Hindu discrimination and oppression. Therefore, Dalit separatism should be understood as a political discourse of minority groups in the context of state formation rather than another partition.

시민민주주의와 보편적 법체계의 발전: 헌법과 국제법을 대체하는 세계법의 수사학

The Constitution is the highest law of the country, while international law is a field of law that deals with the rights and obligations between countries. The essence of international community is of decentralized nature, in which the legal order is formed according to the principle of sovereign equality. However, there are many perspectives that approach the international community and international law from a universalistic and idealistic viewpoint. In other words, if the positivist and pseudo-oriented view of international law is the reality of international community and international law, the universalist or idealist perception of international law can be said to be their goals. It is true that those two perspectives on international community and international law are neither omnicient nor all-perceiving, but complexly intertwined. The Constitution and international law, which can be considered the two axes of public law, are closely interrelated to the formation of a modern absolute state and civic democracy. The absoluteness of state power and civic democracy are doomed to fate our present and our future. This is not only such fundamental political order, but it also has become a foundation for the development of modern and contemporary order of law. And the two dimensions of order, politics and law, are developing in a dialectical manner. Under this background, this paper aims to provide a harmonious view sprucing up the reality of public law that penetrates both of the international and domestic society within a large framework. It is for research purpose and needs an effort of work by reviewing and analyzing the essence, commonalities, and differences among various adjacent concepts of the Constitution and international law discourse. This paper first begins with a discussion by presenting the historical development of existing hard legal system that penetrates the Constitution and international law through their realistic framework. Furthermore, we look at the softness of international law, conceptual discourse on the international law and world law, international constitutionalism and constitutional theory, and a compendium of world administrative law. We look at the background for the development of these commentaries, the main topics of discussion, and their commonalities or differences. Finally we briefly diagnose and place the future of new sermons that needs to be adduced due to changes in the international community.

Estimation of the Structure of Hydrophobic Surfaces Using the Cassie-Baxter Equation.

The effect of extreme water repellency, called the lotus effect, is caused by the formation of a Cassie-Baxter state in which only a small portion of the wetting liquid droplet is in contact with the surface. The rest of the bottom of the droplet is in contact with air pockets. Instrumental methods are often used to determine the textural features that cause this effect-scanning electron and atomic force microscopies, profilometry, etc. However, this result provides only an accurate texture model, not the actual information about the part of the surface that is wetted by the liquid. Here, we show a practical method for estimating the surface fraction of texture that has contact with liquid in a Cassie-Baxter wetting state. The method is performed using a set of ethanol-water mixtures to determine the contact angle of the textured and chemically equivalent flat surfaces of AlSI 304 steel, 7500 aluminum, and siloxane elastomer. We showed that the system of Cassie-Baxter equations can be solved graphically by the wetting diagrams introduced in this paper, returning a value for the texture surface fraction in contact with a liquid. We anticipate that the demonstrated method will be useful for a direct evaluation of the ability of textures to repel liquids, particularly superhydrophobic and superoleophobic materials, slippery liquid-infused porous surfaces, etc.

The Role of Terminal Fluorination on Energy Inversion in Organic Solar Cells.

Suppressing the non-radiative energy loss(ΔE3) mediated by triplet charge transfer stateis crucial for high-performance organic solar cells (OSCs). Here, we decode the energy inversionthroughmulti-scale theoretical simulation, which inhibits the non-emissivetriplet (T1) state formation. However, itis mystified by the system dependence.We first demonstrate a direct relationship of "the probability of Face-on orientation(PFace-on) is proportional to the probability of energy inversion (PEI)", which is related to the function of terminal fluorination. Through Pearson's correlation coefficientand machine learning model, the useful stacking structural parameters were obtained to clarify the effect of π-bridge group on the function of terminal fluorination. Basedon the molecular descriptorsestablished,we explain that the fluorination effect is beneficial to Face-onorientationand thus energy inversiondue tothe enhancedintermolecular coupling.Butthe π-bridge inhibits thiscoupling with the interfacialstacking configuration appearingmore "TT_IC".This work provides a directional standard for promotingenergy inversionto reduceΔE3for the high-performance OSCs.

Study on the interface electronic structure, strain modulation and transport properties of composite heterojunction of 2D semimetal TiS2 and MX2 (M=Mo, W, Cr, Zr, Hf; X=S, Se, Te) semiconductor

Ohmic contacts play a crucial role in realizing high-performance electronic devices based on two-dimensional materials. The contact between semimetals and semiconductors can mitigate the formation of metal-induced gap states (MIGS), thereby reducing the SBH, enhancing the efficiency of high charge injection, and facilitating the establishment of ohmic contacts. This study involves a systematic exploration of the contact characteristics between the two-dimensional semimetal TiS2 and semiconductor MX2 (M = Mo, W, Cr, Zr, Hf; X = S, Se, Te) through first-principles calculations. It is found that the TiS2/MoSe2 and TiS2/WSe2 heterojunction achieve ohmic contact. Investigations into their transport properties reveal that significant currents can be observed at relatively low voltages, indicating excellent transport performance of these heterojunctions. The TiS2/CrSe2 and TiS2/HfSe2 contact heterojunctions also show low Schottky barrier height (SBH), with the barrier height being adjustable under strain. The SBH of TiS2/CrSe2 and TiS2/HfSe2 heterojunctions are very close to zero under stresses of 4 % and −4%, respectively. This also implies that our research can offer valuable guidance for the development of adjustable Schottky nano-devices and high-performance optoelectronic devices.

Legal Framework of State Formation in Lithuania: A Historical Comparison Pre- and Post-EU Integration

The accession of new countries to the European Union (EU) in May 2004 marked a qualitatively new stage in the integration processes both in Europe and worldwide. Analysing the positive and negative phenomena accompanying the enlargement of the EU is significant for countries considering or potentially joining the EU in the future. This analysis is crucial when forming long-term economic policies and deciding their integration directions. The experience of the Republic of Lithuania in studying the impact of external political situations on the processes of integration into the European community is seen as illustrative for Ukraine due to shared initial characteristics and historical proximity between the states. The article analyses the features of Lithuania’s integration into the European community. A significant normative and systemic gap between the periods studied in the context of the legislative field is demonstrated. The study aims to analyse the dynamics of the normative-legal framework in developing European integration and state-building processes in Lithuania from 1990 to 2021. The research identifies which countries had the most significant influence on the state-building process in Lithuania after 1990 during the establishment and development of democratisation. Fundamental concepts of state-building in Lithuania during the studied period and the corresponding normative-legal framework of the process are highlighted. It is established that Lithuania’s accession, despite a solid societal push for integration into the Western political and economic culture, had several distinctive features related to constitutional institutions, significantly impacting the resolution of issues between the government and EU institutions.

Formation of nonclassical and non-Gaussian states of a strong electromagnetic field due to its interaction with free electrons produced by ionization of a target gas

Formation of nonclassical and non-Gaussian states of a strong electromagnetic field due to its interaction with free electrons produced by ionization of a target gas

Cavity-Mediated Enhancement of the Energy Transfer in the Reduced Fenna-Matthews-Olson Complex.

Strong light-matter interaction leads to the formation of hybrid polariton states and can alter the light-harvesting properties of natural photosynthetic systems without modifying their chemical structure. In the present study, we computationally investigate the effect of the resonant cavity on the efficiency and the rate of the population transfer in a quantum system coupled to the cavity and the dissipative environment. The parameters of the model system were chosen to represent the Fenna-Matthews-Olson natural light-harvesting complex reduced to the three essential sites. The dynamics of the total system was propagated using the hierarchical equations of motion. Our results show that the strong light-matter interaction can accelerate the population transfer process compared to the cavity-free case but at the cost of lowering the transfer efficiency. The transition to the strong coupling regime was found to coincide with the degeneracy of polariton eigenvalues. Our findings indicate the potential and the limit of tuning the energy transfer in already efficient natural light-harvesting systems.

Methyl Methacrylate Copolymer with Pendant Thioxanthenone Groups as Active Layer for Resistive Memory Devices.

An electro-active copolymer of methyl methacrylate and 2-((4-acroylpiperazine-1-yl)methyl)-9H-thioxanthene-9-one (poly(MMA-co-ThS)) was synthesized by radical polymerization. The copolymer has good solubility in most organic solvents, thermal stability up to 282 °C and excellent ability to form thin films on silicon wafers. Poly(MMA-co-ThS) films exhibited an electrochemical and electrochromic activity resulting in the formation of long-lived radical anion states of pendant thioxanthone groups inside the film. These states exhibit optical transitions in the visible region as a broad optical absorption band, 500<λ<900 nm (1.38<Wopt(ThS)<2.48 eV) with a maximum at λmax=675 nm (1.84 eV). Using temperature measurements of the current-voltage characteristics of p-Si(100)/poly(MMA-co-ThS)/Al devices, it was shown that the charge transport in the film occurs by a multiphonon mechanism, which is quantitatively described by the Nasyrov-Gritsenko model of phonon-assisted tunneling between traps. The value of the optical transition energy of the trap, determined by the Nasyrov-Gritsenko model, Wopt=1.8 eV, is in a good agreement with Wopt(ThS), confirming the nature of the traps as 9H-thioxanthen-9-one structures. The n++Si(100)/poly(MMA-co-ThS)/Al memory device exhibited a memristive effect (reversible ON/OFF switching of the device) with an initial "forming" cycle followed by repetitive memory cycles characterized by bipolar switching.

Measurement on the fatigue-healing performance of SARAs fractions in bitumen and its characterization by molecular simulations

The objective of this research was to investigate the healing characteristics of bitumen through the assessment of fatigue-healing performance of SARAs fractions and its characterization at the molecular level with SARAs fractions as the intermediate. Firstly, the flow behaviors and fatigue-healing performance of fractions were characterized by rheometer. Then, the diffusion systems were constructed and the diffusion with preset cracks was carried out, the evaluation of which was identified by density distribution, relative concentration in crack region, mean square displacement and interaction effect. The results indicate that aromatics exhibit the closest similarity to original bitumen in flowing behavior, which also reflected in the healing performance. The healing performance of resins and asphaltenes are extremely limited while that of saturates was comparable to fluid. Molecular simulation was further supporting to investigate the healing process. A platform period was found in the healing period when the molecules would move to seek the lowest energy state which was considered as healing in the alternative perspective. During the period, heavy components were more difficult to traverse while weak interaction between light components would shorten the period and identify the lowest energy state more easily, thereby greatly affecting the healing performance of fractions. Furthermore, heavy components are analogous to anchor points, among which resins were more readily aggregated and asphaltenes were relatively dispersed, while light components diffuse flexibly within them. The diffusion has the potential to drive the movement of heavy components which also kept the capture of other components, ultimately resulting in the formation of a stable healing state. The outcome with a discernible interaction effect would be important theoretical significance for the refinement of bitumen of better healing performance and the potential to influence the development of rejuvenators.

Photocatalyst‐Free Wavelength‐Dependant Sequential Ring Transformations of Pyrazolo[1,2‐a]pyrazolones

We report new sequential wavelength‐selective photochemical transformations of 1‐alkenylpyrazolo[1,2‐a]pyrazolones to pyrazolo[1,2‐a][1,2]diazepines or cyclobuta[c]pyrazolo[1,2‐a]pyrazolones. Irradiation of 1‐alkenylpyrazolo[1,2‐a]pyrazolones with visible‐light (blue LED, 457 nm) induced selective ‘ring switching’ transformation into pyrazolo[1,2‐a][1,2]diazepines, which, upon irradiation with UV A light (black LED, 365 nm) underwent electrocyclisation into cyclobuta[c]pyrazolo[1,2‐a]pyrazolones. Due to the very narrow irradiation wavelength now available from OLED sources, the selective formation of either 5,7‐bicyclic or 5,5,4‐tricyclic ring systems from the 5,5‐bicyclic starting material is possible simply by changing the wavelength of the irradiation source. The transformations took place under mild conditions in the absence of additives or photocatalysts. Mechanistic studies indicate that these transformations proceed through the formation of an excited triplet state of the substrate, followed by selective homolytic C(1)–N(8) bond cleavage, intersystem crossing, and cyclization of the zwitterionic intermediate on the ground potential energy surface. Subsequent photoinduced disrotatory stereospecific 4‐π‐electrocyclization of the 5,7‐bicyclic systems leads to 3D‐rich 5,5,4‐tricyclic products.