State Theory Research Articles

The State Theory of Money

The State Theory of Money

An accurate full-dimensional potential energy surface of the hydrogen sulfide dimer system and its kinetics for the hydrogen exchange channel

The hydrogen sulfide cluster exhibits weak interaction, which plays a crucial role in biomolecules, superconductivity, etc. Hydrogen sulfide dimer, (H2S)2, as a relatively simple system containing this interaction, is a preferred subject for studying this weak interaction and has attracted significant attention recently. In this work, an accurate full-dimensional potential energy surface (PES) for the (H2S)2 system is reported using the permutationally invariant polynomial-neural network (PIP-NN) method. The energies for the sampled 106,952 configurations are calculated using the CCSD(T)-F12a/AVTZ method, with the Boys-Bernardi counterpoise method used to eliminate basis set superposition errors (BSSE). The total root-mean square error (RMSE) of the final PIP-NN PES is only 0.019 kcal mol−1. The PES can reproduce well the structures, energies, and harmonic frequencies of the nine stationary points, five stationary isomers and four transition states. Two new hydrogen exchange reaction channels are included in the current PES. The rate coefficients of the hydrogen exchange channels are calculated using both conventional transition state theory (TST) and canonical variational theory (CVT) with the quantum tunneling correction treated by the zero-curvature tunneling (ZCT) and small curvature tunneling (SCT) methods.

Predictive evaluation of hydrogen diffusion coefficient on Pd(111) surface by path integral simulations using neural network potential

Quantum diffusion of hydrogen (H) on palladium (Pd) (111) was studied using two types of path integral simulations: quantum transition state theory (QTST) and ring polymer molecular dynamics (RPMD). The use of an artificial neural network potential trained by density functional theory calculations has made it feasible to perform path integral simulations considering nuclear quantum effects (NQEs) of a many-body Pd-H system with accuracy. The QTST result has shown a clear non-Arrhenius behavior in the diffusion coefficient (D) of H below the temperature of 150–200 K due to the NQEs. Comparing the D on Pd surface and bulk Pd, it was found that surface and bulk diffusion are competitive at high temperature. Consistent with this, it was observed in the RPMD simulation at 800 K that a part of the quantum trajectories of H on the surface bifurcates to the Pd subsurface. As the temperature decreases, the surface diffusion becomes much faster than the bulk diffusion. Furthermore, distinct quantum behaviors of H were identified at the surface and within the bulk. The D values obtained from this study using a “flexible” Pd surface model differed considerably from those previously reported using “frozen” Pd surface models, indicating an important contribution from Pd vibrations coupled with H diffusion. Published by the American Physical Society 2024

Estimation of undrained shear strength of soft clay during surcharge or vacuum preloading

Preloading using either vacuum or fill surcharge is an effective method for the treatment of very soft saturated clay. The preloading will reduce the water content and increase the shear strength of soil. However, when the soil to be treated is very soft, it is difficult to take soil samples for laboratory tests or carry out in situ tests to determine the soil properties including shear strength. Therefore, there is a need to develop an analytical method to estimate the shear strength during preloading. In this paper, a simple correlation among settlement, water content and undrained shear strength using critical state theory is proposed for saturated soil under one-dimensional loading condition to allow the undrained shear strength variation of the soil to be estimated during preloading without testing. Laboratory model test and field monitoring data are used to verify the validity of this method and the proposed correlation is effective to be used as rough estimations on the undrained shear strength of soft clay.

Polyethylene Glycol‐Based Refolding Kinetic Modulation of CRABP I Protein

ABSTRACTCrowding environment has a significant impact on the folding and stability of protein in biological systems. In this work, we have used four different sizes of a molecular crowder, polyethylene glycol (PEG), to analyze the unfolding and refolding kinetics of an iLBP protein, CRABP I, using urea as chemical denaturant. In general, the stability of the native state of the protein is boosted by the presence of crowding agents in the solution. However, our findings show that not only the type of crowder but also the crowder size played a key role in the effects of excluded volume. In case of lower molecular weight of PEG (M.W. 400), even at 200 g/L concentration, only the viscosity effect is observed, whereas for higher molecular weight of PEG (M.W. 1000), both the viscosity effect and excluded volume effect are noticed, and even at a higher concentration (200 g/L) of PEG 1000, the excluded volume predominates over the viscosity effect. Using the transition state theory, we were also able to determine the free energies of activation for the unfolding and refolding studies from their respective rate constants. Additionally, MD simulation studies provide strong support for our experimental observation. Analysis of secondary structure propensity (SSP) reveals a marked decline in the presence of structural elements (β‐sheet, β‐bridge, turn, and α‐helix) from 81% to 43% over the 1 μs time scale unfolding MD simulation under 8 M urea conditions. Conversely, in a 200 ns refolding simulation, the rate of refolding notably increases at a concentration of 200 g/L PEG 1000.

Hydrogen Atom Abstraction Reaction from Silane with Hydrogen and Methyl Radicals: Rate Constants and Kinetic Isotopic Effects.

The thermal rate constants and H/D kinetic isotope effects (KIEs) of the reactions SiH4 + H SiH3 + H2 and SiH4 + CH3 SiH3 + CH4 were calculated with the variational transition state theory including multidimensional tunneling corrections (VTST-MT). The ωB97X-D and CCSD(T) methods were employed to compute the barrier height and reaction energy. The ωB97X-D/aug-cc-pVTZ methodology was used to build reaction paths, and the CCSD(T)/CBSQ-5 approach was used to improve the energetics of the stationary points in the calculations of CVT/μOMT thermal rate constants. For the SiH4 + H pathway, the CVT/μOMT rate constants and H/D KIEs are in excellent agreement with previous experimental and theoretical calculations; otherwise, for the SiH4 + CH3 pathway, which has few experimental and theoretical data available, it has provided, for the first time, rate constants and kinetic isotope effects using variational transition state theory with multidimensional tunneling corrections.

Theoretical research of the NO and N2O reduction by char in oxy-fuel CFBC: Influence of H2O

Oxy-fuel CFBC has lower NOx emissions compared to air combustion, with the high H2O content affecting NO and N2O reduction. This study, using density functional theory and transition state theory, investigates the impact of H2O on the char model at the electronic level and its subsequent influence on NO and N2O reduction. Results reveal that H2O adsorbs onto the active site on char, forming hydroxyl groups and free H atoms. The unstable O atom in –OH group leads to benzene ring rearrangement in the char model, creating additional active sites. NO reduction follows two paths: producing CO(R1) or CO2(R2). For N2O reduction(R3), N2O reduction precedes benzene ring cracking, with CO2 production providing more active sites. In R1, CO formation limits reactive sites and increases activation energy, while R2 and R3 favor CO2 formation. Reaction pathways leading to CO2 formation show lower activation energies and higher pre-exponential factors for N2 release.

Kinetic study of the growth of PAHs from biphenyl with the assistance of phenylacetylene

Biphenyl is a crucial precursor to polycyclic aromatic hydrocarbons (PAHs), and phenylacetylene is an abundant product in aromatic hydrocarbons combustion. By exploring the reaction kinetics of phenylacetylene with biphenyl radicals, we further explore the novel hydrogen-abstraction phenylacetylene-addition (HAPaA) mechanism which is recently proposed to account for alternative mass growth pathways of PAHs. A combination of M06–2X/6–311+G(d,p) and PWPB95-D3/def2-QZVPP calculations were performed to construct the potential energy surfaces, and the rate coefficients were determined via solution of transition state theory based master equations. We demonstrate the capability of biphenyl species to grow with the assistance of phenylacetylene by unraveling the ring growth process of biphenyl radicals, establishing the main evolution routes of key intermediates, and quantifying the competition relationship between various channels. Energetic analysis and kinetic calculations demonstrate that the initial orientations of the reacting moieties do have a remarkable impact on the detailed kinetics of the entrance channels. However, the two adducts formed from initial additions achieve a rapid equilibrium because of the largest rate constants of the interconversion reactions between them, which counteracts the orientation effect on the overall kinetics. Further reaction pathways and corresponding products are related to the aryl radical position. Specifically, the aromatics of 4-phenylphenanthrene or phenanthrene, formed through cyclization reactions followed by hydrogen or phenyl eliminations, are preferred for the “armchair” type 2-biphenyl radical. In contrast, products featuring a triple bond generated through CH β-scission reactions are favored for the “free” type 3-biphenyl and 4-biphenyl radicals. The present research can serve as a good basis for further experimental and modeling studies of PAHs and soot formation.

Real-Time TDDFT Using Noncollinear Functionals.

Recently, we proposed a method to generalize collinear functionals to noncollinear functionals, called multicollinear approach, which has been applied in density functional theory (DFT) and linear-response time-dependent DFT (TDDFT) for the ground state and excited states calculations, respectively. In this work, we demonstrate the application of this method in real-time TDDFT by simulating electronic absorption spectra, Rabi resonance, and precession of a two-magnetic center system. Thanks to the nonvanishing local exchange-correlation torque provided by multicollinear functionals, research into the torques in the evolution of magnetization vector is carried out, which is useful for the exploration on spin dynamics.

NO2 properties that affect its reaction with pristine and Pt-doped SnS2: a gas sensor study.

The reaction of NO2 with pristine and Pt-doped SnS2 surfaces is investigated theoretically and compared with the experiment. Transition state theory formalism for gas sensors is adopted to present NO2 gas sensing. The dissociation temperature at approximately 150 °C is found to be of great importance in NO2 reactions. The adsorption and transition states of NO2 with pristine and Pt-doped SnS2 are calculated. Pt doping includes 0.5, 1, and 1.5% in accordance with available experimental results. The variation of thermodynamic quantities such as Gibbs free energy with Pt concentration and temperature is calculated. Transition state theory parameters that are suitable for the present sensor are determined. The results include the variation in response time with temperature, Pt concentration, and NO2 concentration. Response and response time as a function of temperature are rarely investigated in theoretical calculations, which is one of the advantages of the present study. Optimum response temperature and Pt concentration are found. The results agree with available experimental results. Density functional theory at the B3LYP level optimize molecular structures. 6-311G** basis set is used for all elements except Sn and Pt treated using SDD basis set. Gaussian 09 program and its facilities are used to perform present optimizations.

A DFT-based kinetic equation for Co3O4 decomposition reaction in high-temperature thermochemical energy storage

Thermal energy storage supports stable grid integration of variable renewable energy sources by reducing power curtailment and generation costs. Thermochemical energy storage (TCES) offers high energy density and long-duration, long-distance storage advantages, making it a focus in large-scale applications such as concentrated solar power plants. Metal oxide systems like Co3O4/CoO are widely used due to their operational flexibility, yet limited understanding of their decomposition kinetics hinders optimization of TCES materials and reactor design. In this study, we developed a rate equation based on density functional theory and transition state theory to identify the reaction mechanisms and rate constants at the gas–solid interface, prior to predict Co3O4 decomposition kinetics. A microkinetic model was then constructed to couple surface reactions with oxygen ion diffusion across the bulk, which was integrated into a reactor model accounting for mass transfer steps. The model’s accuracy was validated against the data from the micro-fluidized bed thermogravimetric analyzer experiments. For particles smaller than 150 μm, the formation step of adsorbed O2 (energy barrier of 0.8 eV) controls the reaction rate, while gas diffusion dominates the reaction rate for particles larger than 500 μm. To conclude, the optimal conditions for maximizing charge–discharge kinetics in TCES applications were identified as: 850–900 °C, 0–10 vol% O2, and 150–500 μm. This model provides theoretical guidance for optimizing TCES materials and reactor design, reducing experimental costs while maintaining accuracy.

Reproduksi Budaya Pambiwara dalam Upacara Pernikahan Adat Jawa

This article explores the efforts of Sanggar Permadani in developing, preserving, and sustaining Javanese culture. The primary focus of the Javanese cultural heritage preserved by Sanggar Permadani is pambiwara, individuals responsible for organizing and guiding traditional Javanese ceremonial events. This preservation is crucial as fewer people are performing traditional Javanese wedding ceremonies and employing the services of pambiwara. This qualitative study employs an ethnographic approach, with data collected through observations, interviews, and documentation. The findings reveal that Sanggar Permadani has successfully preserved Javanese culture by training new generations of pambiwara through annual courses or training sessions held over five months. All participants are of Javanese descent and come from diverse educational backgrounds. To date, Sanggar Permadani has graduated 20 cohorts. The findings align with Pierre Bourdieu’s theory of cultural capital and embodied state, which posits that individuals shape their identity based on cultural capital and educational investment imparted from birth.

Are human brain organoids cloned human individuals? An ethical analysis

In recent years, there has been much ethical debate about human brain organoid research. However, the possibility that human brain organoids might be human individuals has not been examined. This is an important issue because if human brain organoids are human individuals, then the creation of human brain organoids could be a form of human reproductive cloning. We examine the implications of two mainstream bioethical views on the nature of human individuals for human brain organoids: (1) Functional Integration Theory, the view that the capacity to integrate vital functions is the criterion for human individuality, and (2) Mental State Theory, the view that some mental capacity is the criterion for human individuality. We find that under either theory of human individuality, human brain organoids could be human individuals in the future. According to a version of Functional Integration Theory that locates the integrative function in the human brainstem (Brainstem Theory), a well-developed human brainstem organoid can be a human individual. Further, on Mental State Theory, a human brain organoid with certain mental capacities can be a human individual. Our results, combined with the ban on human reproductive cloning, may provide some reasons to be more cautious in human brain organoid research. Alternatively, in light of the progress in human brain organoid research, it may be necessary to reconsider the ethics and laws surrounding human reproductive cloning. This research paves the way for the first time to examine the question of great ethical importance whether human brain organoids can be human individuals, and encourages further consideration.

Kinetic and Thermodynamic Aspects of the Degradation of Ferritic Steels Immersed in Solar Salt

The study and improvement of the corrosion resistance of materials used in concentrated solar power plants is a permanent field of research. This involves determining their chemical stability when in contact with heat transfer fluids, such as molten nitrate salts. Various studies indicate an improvement in the corrosion resistance of iron-based alloys with the incorporation of elements that show high reactivity and solubility in molten nitrate salts, such as Cr and Mo. This study analyzes the kinetic and thermodynamic aspects of the beginning of the corrosion process of ferritic steels immersed in Solar Salt at 400, 500, and 600 °C. The analysis of the kinetic data using the Arrhenius equation and the Transition State Theory shows that an increase in the Cr/Mo ratio reduces the activation energy, the standard formation enthalpy, and the standard formation entropy. This indicates that its incorporation favors the degradation of steel; however, the results show a reduction in the corrosion rate. This effect is possible due to a synergistic effect by the formation of insoluble Fe-oxide layers that favor the formation of a Cr oxide layer at the Fe-oxide-metal interface, which limits the subsequent oxidation of Fe.

Key issues of Marxist Doctrine on the State in the First Half of the 20th Century

The article examines the evolution of Marxist state theory in the first half of the 20th century, with particular emphasis on the period following the October Revolution of 1917. The author analyzes key aspects of Marxist-Leninist doctrine on the state, including the concept of the dictatorship of the proletariat, the issue of eliminating class differences between peasantry and workers, and questions of overcoming commodity forms and bureaucracy. The study investigates both theoretical and practical aspects of socialist construction in the conditions of a backward agrarian country, which Russia was at the time. Special attention is given to the analysis of works by V. I. Lenin, J. V. Stalin, L. D. Trotsky, I. Bukharin, and other Marxist theorists. The article examines mechanisms facilitating the movement towards a class less society and analyzes specific manifestations of the state’s withering away during the process of socialist construction. The study draws conclusions about the developmental trends of the socialist state and the role of the dictatorship of the proletariat in this process. The article emphasizes the dialectical relationship between the theoretical propositions of Marxism and their practical implementation in specific historical conditions.

The Legal and State Theory Problem of Federal Somalia in the 21st Century

Somalia is one of the most unstable states in Africa, and this instability is the result of power-political rivalries, due to the historical influences of different eras. Three separate entities with the capacity to influence the state can be distinguished: the oldest is the Somali clan system and hence the clans, followed by the current end product of the significant Islamic expansion in the region, the jihadist organisation al-Shabaab, and finally the Somali government, which is the main enforcer of the federal state apparatus. My aim is to examine the triad’s relationship and the extent of their power from a legal and state-theoretical perspective, which requires a descriptive analysis of the actors in order to reveal their legal and state-theoretical implications. The study concludes that all three actors are in varying relationships with each other, which may be a hostile relationship or a state of dependency, and this is at the root of Somalia’s instability, the resolution of which will be a long-term process.

Structure-performance relationship and molecular structure optimization design of acid phosphate ester extractants

The extraction performance of acid phosphate ester extractants (PEEs) decreases significantly as the acidity of the aqueous phase increases. Therefore, finding PEEs suitable for high-acid environments has become critical to addressing their performance attenuation. However, the unclear structure-performance relationship of PEEs has led to a lack of guidance in experimental synthesis, significantly impeding the emergence of new acid-resistant PEEs. To tackle these issues, ten novel phenyl phosphate ester extractants were designed based on the molecular formula of phosphodiester (R1R2P(=O)OH) and the conjugation effect of the benzene ring. The relationship between the intrinsic extraction performance of acid PEEs and substituent groups (phenoxy, alkoxy, and alkyl) was quantitatively established by calculating the Gibbs free energy changes of three primary reactions (dimer dissociation, monomer acid ionization, and metal coordination) during divalent cobalt ion extraction. Additionally, the impact of different substitution sites (para, meta, and ortho) of the benzene ring on the extraction performance of acid PEEs was studied. The results indicated that introducing phenoxy groups into traditional acid PEEs (P204 and P507) can effectively enhance the extractants’ acid ionization ability and thermodynamic driving force. The extraction performance of acid PEEs is positively correlated with the number of phenoxy groups, and carbon chain substitution at the meta-position of the benzene ring is the most advantageous. By screening five low-toxicity and low-cost phenolic hydroxyl reagents currently available on the market, design a phenyl phosphate ester extractant ([(CH3)3CCH2C(CH3)2C6H4O]2P(=O)OH, P-4TO) that combines cost and performance advantages. Furthermore, the transition state theory was used to confirm the feasibility of preparing P-4TO, which provided a comprehensive theoretical research method for the future design and synthesis of efficient PEEs.

Banditry and human security in Nigeria: Assessing the amnesty implemetation in the North-West region

ABSTRACT Existing studies on banditry in Nigeria have blamed it on bad governance, ungoverned spaces and a failed state thesis among others. However, little academic discourse has been conducted to cover the gap between amnesty implementation for bandits and how it undermines human security in North-West Nigeria. While predominant bandit-ridden states in the region have opted to grant amnesty to repentant bandits, against the federal implementation of a more kinetic approach, this strategy seems to have failed to tackle rising banditry and its attendant threat to human security. Adopting a descriptive qualitative research and anchoring it on the fragile state theory, the paper argues that the failure of amnesty stems from the transactional nature of the programme, born out of the complicity of state representatives and bandits, which consequently was unable to prevent the so-called ‘repentant bandits’ from returning to crime. As a result, the amnesty failed to tackle the persistent bandit attacks and associated humanitarian crisis. While the finding of this paper queries the way and manner the amnesty was implemented, it recommends adopting a strategic kinetic approach with strict rules of engagement that will be clearly spelt out and adhered to by the parties involved.

High-Level Calculation for Assessing the Atmospheric Reactivity of Pentachlorophenol with Hydroxyl Radical: Mechanism and Kinetics.

This work aims to investigate the reactivity of the pentachlorophenol (PCP) compound, C6Cl5OH, with a hydroxyl (OH) radical in the gas phase. Geometry optimizations and vibrational frequency calculations were performed using DFT-M06-2X/6-311++G(d,p). Single-point energy calculations were carried out using the single-reference coupled cluster method, specifically CCSD(T), and the multiconfigurational CASPT2 level of theory to characterize the atmospheric degradation processes of PCP with OH radicals and to identify which chemical species resulting from their decomposition could remain in the gas phase. The performance of various families of basis sets was tested. The widely used augmented-correlation-consistent basis set family aug-cc-pVXZ-DK (X = D, T, and Q) was compared to the atomic natural orbital basis sets ANO-RCC-VXZP (X = D, T, and Q). The energy profile at 298 K showed that the Cl- and OH-abstractions are not energetically favorable. H-abstraction and OH-addition/Ck (k = 1-6) are characterized by the lowest Gibbs energies of activation and are strongly exothermic. The canonical transition state theory (TST) with a simple Wigner tunneling correction is used to predict the rate constants over the 220-400 K temperature range for each reaction channel. The overall rate constant at 298 K based on our calculations is about 3.25 × 10-13, 3.10 × 10-15, and 2.21 × 10-15 cm3 molecule-1 s-1 at M06-2X, CASPT2/ANO-RCC-VQZP, and CASPT2/aug-cc-pVQZ-DK levels of theory, respectively. The PCP atmospheric lifetime at 298 K is predicted to be in the range from 1 to 12-16 years at 0 km in the presence of variable OH concentration (9.00 × 105 to 1.50 × 107 molecules cm-3) based on CASPT2 data.

Evgeny Bronislavovich Pashukanis as a legal theorist

The article analyzes the work of the famous Russian legal scientist, academician E. B. Pashukanis, whose name is most directly connected with the formation of the Soviet theory of state and law, the solution of important issues of doctrinal support for state building in the 1920s – 1930s and the formation of the Soviet legal system. The focus of this study is on the main problems of the content, nature and focus of E. B. Pashukanis’ legal views, the place of his exchange theory of law in the history of political and legal thought. From a methodological point of view, it is important to use modern historiographical approaches to illuminating and analyzing the history of political and legal thought, which allows us to show the specifics of the legal views of an outstanding Soviet lawyer not only as a moment of formation and development of the Soviet theory of states and law, but also from the perspective of continuity and novelty relative to predecessors and contemporaries, in the light of foreign sources, clarification semantic characteristics of scientific language in his works. Along with the methodological aspects, the novelty of the study also lies in the significant clarification of some basic provisions of E. B. Pashukanis’ legal ideas, related, in particular, to the idea of the “extinction of law” in the conditions of the victorious proletarian revolution and the construction of a socialist society, focusing on the theoretical and cognitive techniques of German lawyers of the second half of the XIX century.