State Theory Research Articles

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.

Stressing state analysis of unbonded prestressed concrete simply supported slabs in fire

AbstractThis paper reveals the essential stressing state characteristics of unbonded prestressed concrete (UPC) simply supported slabs in fire by exploring the experimental data based on structural stressing state theory. First, the experimental deflections are transformed into the generalized work of force values to represent the structural characteristic parameter. Then, the Mann–Kendall criterion detects the mutation points where the characteristic parameter curve shows a trend change with the rising temperature. Next, the mutation characteristics are verified by studying the stressing state modes and coordinative working behavior of simply supported slabs under characteristic temperatures. Consequently, the elastoplastic branch points and failure starting point of the simply supported slabs in fire are revealed, complying with the natural law from quantitative change to qualitative change. Finally, the formula is fitted to calculate the failure loads with a verification, and the existing failure loads were redefined to provide a new and valuable reference for analyzing the working behavior of UPC simply supported slabs in fire.

Fluorination Affects the Force Sensitivity and Nonequilibrium Dynamics of the Mechanochemical Unzipping of Ladderanes.

When multiple reaction steps occur before thermal equilibration, kinetic energy from one reaction step can influence overall product distributions in ways that are not well predicted by transition state theory. An understanding of how the structural features of mechanophores, such as substitutions, affect reactivity, product distribution, and the extent of dynamic effects in the mechanochemical manifolds is necessary for designing chemical reactions and responsive materials. We synthesized two tetrafluorinated [4]-ladderanes with fluorination on different rungs and found that the fluorination pattern influenced the force sensitivity and stereochemical distribution of products in the mechanochemistry of these fluorinated ladderanes. The threshold forces for mechanochemical unzipping of ladderane were decreased by α-fluorination and increased by γ-fluorination; these changes correlated to the different stabilizing or destabilizing effects of fluorination patterns on the first transition state. Using ab initio steered molecular dynamics (AISMD), we compared the product distributions of synthesized and hypothetical ladderanes with different substitution patterns. These calculations suggest that fluorination on the first two bonds of ladderane gives rise to a larger fraction of dynamic trajectories and a larger fraction of E-alkene product through a mechanism resulting from larger momentum because of the greater atomic mass of fluorine. Fluorination on the third and fourth rungs instead gives a larger fraction of E-alkene product primarily due to electronic effects. These combined experimental and computational studies of the mechanochemical unzipping of fluorinated ladderanes provide an example of how relatively simple substituents can affect the extent of nonstatistical dynamics and, thus, mechanochemical outcomes.

Quantum Chemistry Study on Cl-Initiated Reactions of 2-Chloropropane and 2-Methylpropanoyl Halogen (Cl, Br, F): Mechanism, Kinetics, and Atmospheric Implications.

Halogenated volatile organic compounds (HVOCs) pose significant bioaccumulative and toxicological risks, necessitating effective strategies for their removal. Here, we show, through a computational study employing density functional theory and coupled cluster methods, the detailed mechanism and kinetic properties of Cl-initiated degradation reactions of 2-chloropropane (2-CP, (CH3)2CHCl) and 2-methylpropanoyl halide ((CH3)2CHCOX, X = Cl, Br, F). The reaction rate constants of all the channels were calculated by the canonical variational transition state theory (CVT) with the correction of the small curvature tunneling effect (SCT) at 200-1000 K. The subsequent transformation pathways of the major radical products of (CH3)2CHCl and (CH3)2CHCOCl in the presence of O2, NO, and HO2 radical were investigated. The results elucidate the reaction pathways and rate constants, which are in excellent agreement with the experimental data at 296 K. We further explore the atmospheric implications of these reactions by assessing the atmospheric lifetime (τ) and ozone depletion potential (ODP). Additionally, we delve into the aquatic toxicity and bioaccumulation potential of the reactants and their transformation products. This study not only advances our knowledge of the atmospheric fate of halogenated hydrocarbons but also underscores the importance of considering the environmental and toxicological impacts in the development of HVOC mitigation strategies.

Semiclassical instanton theory for reaction rates at any temperature: How a rigorous real-time derivation solves the crossover temperature problem.

Instanton theory relates the rate constant for tunneling through a barrier to the periodic classical trajectory on the upturned potential energy surface, whose period is τ = ℏ/(kBT). Unfortunately, the standard theory is only applicable below the "crossover temperature," where the periodic orbit first appears. This paper presents a rigorous semiclassical (ℏ → 0) theory for the rate that is valid at any temperature. The theory is derived by combining Bleistein's method for generating uniform asymptotic expansions with a real-time modification of Richardson's flux-correlation function derivation of instanton theory. The resulting theory smoothly connects the instanton result at low temperature to the parabolic correction to Eyring transition state theory at high-temperature. Although the derivation involves real time, the final theory only involves imaginary-time (thermal) properties, consistent with the standard version of instanton theory. Therefore, it is no more difficult to compute than the standard theory. The theory is illustrated with application to model systems, where it is shown to give excellent numerical results. Finally, the first-principles approach taken here results in a number of advantages over previous attempts to extend the imaginary free-energy formulation of instanton theory. In addition to producing a theory that is a smooth (continuously differentiable) function of temperature, the derivation also naturally incorporates hyperasymptotic (i.e., multi-orbit) terms and provides a framework for further extensions of the theory.

Semiclassical Transition State Theory (SCTST) Rate Coefficients for the Unimolecular Decomposition of the Ethoxy (CH3CH2O) Radical.

The thermal unimolecular decay of ethoxy is important in high-temperature combustion environments where the ethoxy radical is a key reactive intermediate. Two dissociation pathways of ethoxy, including the β-C-C scission to yield CH3 + CH2O and the H-elimination to make H + CH3CHO, were characterized using a high-level coupled-cluster-based composite quantum chemical method (mHEAT-345(QΛ)). The former route is found to be dominant while the latter is insignificant, in agreement with previous experimental and theoretical studies. Thermal rate coefficients are calculated for P = 0.001-658 atm (of air) and T = 300-2500 K using semiclassical transition state theory (SCTST) in combination with a pragmatic two-dimensional E,J-resolved master equation (2DME). The effects of tunneling and anharmonicity on the calculated rate constants are also examined. The tunneling factor is found to be inversely dependent on pressure, contrary to previous observations of pressure-dependent tunneling in entrance channels.

Enhancing Eyringpy: Accurate Rate Constants with Canonical Variational Transition State Theory and the Hindered Rotor Model.

The recrossing effect and hindered rotations can lead to significant inaccuracies in rate constant calculations using transition state theory and the harmonic oscillator approximation. To address these issues, we enhanced Eyringpy, a Python-based computational tool, by integrating the canonical variational transition state theory (CVT) and the hindered rotor model, effectively mitigating the limitations of traditional methods. CVT rate constants are calculated using electronic structure data from nonstationary points along the minimum-energy path. Additionally, we developed an algorithm based on reaction force analysis to autonomously select relevant nonstationary points. Torsions are modeled using one-dimensional hindered rotor approaches proposed by Pitzer-Gwinn and Ayala-Schlegel.

Only time will tell: How teams centralize their voice around competent members over time to perform better

SummaryWe posit that time significantly impacts how voice—members' expression of work‐related ideas—becomes unequally distributed within teams. Building upon insights from expectation states theory (EST), we propose that over time, voice becomes more centralized in teams, especially around members who are more competent than others. Moreover, we argue that teams whose members are higher in conscientiousness or openness to experience are better able to place more competent members in central speaking roles early on as well as progressively replace less competent members with more competent ones in those roles. Finally, we predict that, in comparison to teams that have egalitarian voice distributions, those that end up with more centralized voice distributions perform better when they give their most competent members more dominant speaking roles and perform worse when they do not. We found general support for these arguments in a study using four waves of data collected over time from 175 student project teams. Thus, we highlight how voice centralization does not always have negative consequences for teams but can benefit teams in certain circumstances. We discuss the implications of our findings for theory and practice.

Systematic study on the hydrogen abstraction reactions from oxygenated compounds by H and HO2

AbstractTo extend the rule‐based approach for hydrogen abstraction reactions from oxygenated compounds, a systematic investigation was performed to examine the reactivity of gas‐phase hydrogen abstraction reactions from alkyl groups (methyl and ethyl groups) bound to oxygen atoms in five types of oxygenated compounds (alcohols, ethers, formate esters, acetate esters, and carbonate esters) by H atoms and HO2 radicals comprehensively considering rotational conformers. Quantum chemical calculations were conducted at the CBS‐QB3 level for stationary points. Rate constants were determined employing conventional transition state theory (TST). For hydrogen abstraction reactions by H, the rotational conformer distribution partition function was employed to approximate partition functions, owing to the similarity in vibrational energy‐level structures among conformers. In hydrogen abstraction reactions by HO2, the vibrational structures of transition‐state (TS) conformers varied significantly due to the hydrogen bonding, leading to an inappropriate evaluation of rate constants when using the lowest‐energy conformer as a representative. Therefore, the rate constants were calculated by the multi‐structural TST. It was revealed that the differences in functional groups containing O atoms mainly affect the bond dissociation energies of the C–H bonds and the activation energies of hydrogen abstraction reactions only when the C atoms are adjacent to the O atoms. Additionally, it was found that hydrogen bonds formed in the TSs show minor effect on rate parameters for the overall rate constants, apart from the reduction of the pre‐exponential factors for the H‐abstraction reactions from the methylene position of ethyl groups. The comparison with the rate constants from previous studies showed reasonable results, indicating that the rate constants in this study, which thoroughly consider rotational conformers, can be the current best estimates.

Research on the Efficacy of Markov Chains in Analyzing and Predicting Chemical Reaction Rates

Abstract. The Markov chain is a powerful mathematical model used to describe stochastic processes in which the probability of each event depends only on the state attained in the previous event. The chemical reaction rate is a measure of how quickly or slowly a chemical reaction proceeds in multiple stages. This research paper uses the case study of enzymes to investigate the efficacy of the Markov chain in analyzing and predicting chemical reaction rates. By modeling chemical reaction pathways using Markov chains, this study tries to explore how Markov chains help capture and predict a chemical systems dynamic behavior. Scientists have been using multiple methods to predict chemical reaction rates, which involve methods like the Arrhenius equation, transition state theory, molecular dynamics, quantum mechanics, and machine learning. In conclusion, after comparing the advantages and disadvantages of the Markov chain predicting method with those methods above, Markov chains did stand out and provide valuable insights into the understanding of reaction dynamics.

Mechanistic studies on the oxidation reaction of n-pentane

The oxidation reaction mechanism of n-pentane is investigated using density functional theory and transition state theory as a case study to elucidate the combustion characteristics of liquids with low boiling points. This study divides the oxidation reaction of n-pentane into four steps. First, n-pentane decomposes to form n-pentyl radicals C5H11 and H, CH3 and C4H9, and C2H5 and C3H7 radicals. Second, n-pentane primarily undergoes H-abstraction reactions with H, CH3, C2H5, and C3H7 radicals to form the C5H11 radicals. Subsequently, C5H11 radicals react with O2 in an addition reaction to form n-pentyl peroxy radicals ROO. Finally, ROO radical undergoes internal H-atom transfer to form hydroperoxy pentyl radicals QOOH, which then undergoes cyclization and bond scission to produce cyclic ethers, alkenes, aldehydes, OH radicals, and HO2 radicals. Results indicate that n-pentane readily decomposes into C2H5 and C3H7 radicals, with a bond dissociation energy of 367.1 KJ/mol. The H-abstraction reactions involving H and CH3 radicals have the fastest rates, which require the lowest energy barriers of 21.6 and 41.9 KJ/mol, respectively. The reaction between C5H11 and O2 is a barrierless addition reaction. The oxidation of n-pentane, which leads to the formation of 2-methyloxirane and OH radicals, exhibits the fastest reaction rate.

Correlative Activation Free Energy (CAFE) Model: Application to Viscous Processes in Inorganic Oxide Glass-Formers

We explore the concept of correlative activation free energy (CAFE) for the analysis and interpretation of viscosity data of a collection of 847 inorganic oxide glass formers that exhibit various degrees of non-Arrhenius behavior. The CAFE model formalism is strictly based on transition state theory and accounts for the variation in the activation barrier for the viscous dissipation due to the structural evolution the system undergoes upon traversing the glass transition regime. Thus, fitting parameters are meaningful in a statistical thermodynamic context. Compared to the VFT and MYEGA equations, fits using the CAFE model are more robust when extrapolating to infinite temperature because the latter encodes non-enthalpic contributions to the rate coefficient more realistically. The CAFE model-based analysis reveals a strong connection between melt fragility and the degree of change in the potential energy landscape with temperature. Accordingly, while the average ground-state potential energy of the glass forming liquid gradually increases with temperature, the energy of the activated state remains relatively invariant. Our analysis also allows one to estimate the number of atoms involved in the viscous relaxation process, which ranges from approximately 10 to 50 atoms for the oxide glass formers studied. We observe that thermally activated dynamic phenomena exhibited by glassy networks, such as the mixed alkali effect, persist into the supercooled liquid state.

Reduced Cost Computation and Exploitation of Accurate Radial Interaction Potentials for Barrier-Less Processes.

Barrier-less steps are typical of radical and ionic reactions in the gas-phase, which often take place in extreme environments such as the combustion reactors operating at very high temperatures or the interstellar medium, characterized by ultralow temperatures and pressures. The difficulty of experimental studies in conditions mimicking these environments suggests that computational approaches can provide a valuable support. In this connection, the most advanced treatments of these processes in the framework of transition state theory are able to deliver accurate kinetic parameters provided that the underlying potential energy surface is sufficiently accurate. Since this requires a balanced treatment of static and dynamic correlation (which play different roles in different regions), very sophisticated and expensive quantum chemical approaches are required. One effective solution of this problem is offered by the computation of accurate one-dimensional radial potentials, which are then used to correct the results of a Monte Carlo sampling performed by cheaper quantum chemical approaches. In this paper, we will show that, for a large panel of different barrier-less reaction steps, the radial potential is ruled by the R-4 term and that addition of a further R-6 contribution provides quantitative agreement with the reference points. The consequences of this outcome are not trivial, since the reference potential can be fitted by a very limited number of points possibly with a nonlinear spacing. In the case of reaction steps ruled by long-range transition states, generalized expressions are also given for computing reaction rates in the framework of the phase-space theory. All these improvements pave the way toward the computation of reaction rates for barrier-less reactions involving large molecules.

Decarbonization and the Capitalist State

ABSTRACTDecarbonization is the most important challenge of our time. Though quite modest, states are taking more climate action. How should we approach these efforts? Sociologists have paid less attention to decarbonization overall but frameworks in political sociology can make sense of state power and climate politics. In this review, I first discuss two sets of literature. The first extends “state‐capacity” and institutionalist frameworks. The second is based on radical and Marxist state theories. Following this, I draw from Mann's concept of “infrastructural power” which combines elements of both and can situate state power in a transnational context. Using this concept and recent literature in political economy, I discuss three infrastructures—finance, trade, and energy—and consequential ways states have altered them in recent years. These actions reveal profound geoeconomic contradictions which will undermine decarbonization. Together, this review provides a wide survey of state theories and macroscopic climate politics with the hope of spurring further discussion and debate.

Efficient Energy Transfer Enabled by Dark States in van der Waals Heterostructures.

Dark exciton states show great potential in condensed matter physics and optoelectronics because of their long lifetime and rich distribution in band structures. Therefore, they can theoretically serve as efficient energy reservoirs, providing a platform for future applications. However, their optical-transition-forbidden nature severely limits their experimental exploration and hinders their current application. Here, we demonstrate a universal dark state nonlinear energy transfer (ET) mechanism in monolayer WS2/CsPbBr3 van der Waals heterostructures under two-photon excitation, which successfully utilizes the enormous energy reserved in the dark exciton state of CsPbBr3 to significantly improve the photoelectric performance of monolayer WS2. We first propose the scenario of resonant ET between the dark state of CsPbBr3 and WS2, and then reveal that this is a typical Förster resonant ET and belongs to the 2D-2D category. Interestingly, the dark state ET in CsPbBr3 is identified as a long-range donor-bridge-acceptor hopping mode, with a potential distance exceeding 200 nm. Finally, we successfully achieve nearly an order of magnitude enhancement in the near-infrared detection performance of monolayer WS2. Our results enrich the theory of dark exciton states and ET, and they provide a way of using dark exciton states for future practical applications.

Coherent control of dressing interaction of sequential-doubly-dressed four-wave mixing

Abstract We investigate the coherent control of dressing interaction in four-wave mixing (FWM) in a Y-type four-level atomic system based on the dressed states theory. We study the density matrix equation acted by two dressing fields simultaneously governing FWM signal intensity and the eigenvalues under the dressed state formalism. It is shown that the peak position and intensity of Autler–Townes splitting both originate from the dressing interaction as the detuning of the probe field is scanned. Moreover, it is observed that the interaction could be controlled by the dressing fields. Such flexibly controlled nonlinear signal has potential applications in optical communication and quantum information processing.

“Twists and Turns”: Chief Leabua Jonathan and Cross-Border Collaborations with South Africa, 1965–1976/7

Chief Leabua Jonathan’s term as prime minister of Lesotho (then Basutoland) began in 1965, the year before the nation’s independence from Britain. During his tenure, he remained one of the few regional leaders whose leadership until the end of his term in 1976/7 was marked by a pattern of inconsistency and contradiction towards apartheid South Africa. This article attempts to illuminate the nexus between his relationship with South Africa and the consequences thereof. Furthermore, it discusses how the mid-1960s and late 1970s became a crucial period for his leadership. His prime ministership and the “twists and turns” in his foreign policy vis-à-vis South Africa are discussed. Here the diplomatic role he played within the ambit of “small states theory” and his country’s foreign policy is investigated. The article shows how under Jonathan, state politics and regional cross-border struggles and collaborations led to disputes regarding the sovereignty of Lesotho.

Comparison of integral equation theories of the liquid state

Comparison of integral equation theories of the liquid state

Impact Evaluation Adoption Towards Coastal Communities with Ongoing East Coast Rail Link (ECRL) in Terengganu

Objective: This article focuses on ongoing ECRL development challenges in Terengganu, Malaysia, by adapting the All-Party Parliamentary Group Malaysia on Sustainable Development Goals (APPGM-SDG) impact evaluation framework, which can serve as a tool for policy intervention in reducing inequality and promoting partnership. Theoretical Framework: The role of the state theory, as applied to explain the initiative launched through state coordination, requires a multistakeholder approach or structuration process in order to assess the impact on the beneficiary's sustainability. Method: The methodology adopted for this research has included in-depth interviews, observations, and site-visit approaches with local people and authoritative informants, and is heavily supported by desk research. Results and Discussion: The result shows that local coastal communities of several towns in Setiu, Terengganu, are positively accepting of this ECRL development. Nevertheless, collaboration and further information are also needed to make themselves compatible with socioeconomic changes. Research Implications: The critical APPGM-SDG mechanism, based on its success story in terms prior impact evaluation, should be embraced in assessing ongoing ECRL and its development through government-to-government partnerships. Originality/Value: This study led to the three imperatives recommendations on the academic context of the development corpus, advocacy, and policy moral deliverables.

A Transition State Theory-Based Continuum Plasticity Model Accounting for the Local Stress Fluctuation

Based on the transition state theory, a continuum plasticity theory is developed for metallic materials. Moreover, the nature of local stress fluctuation within a material point is considered by incorporating the probability distribution of the stresses. The model is applied to investigate the mechanical behaviors of 316 L stainless steel under various loading cases. The simulated results closely match the results obtained by the polycrystal plasticity model and experiments. The mechanical behaviors associated with strain rate sensitivity, temperature dependence, stress relaxation, and strain creep are correctly captured by the model. Furthermore, the proposed model successfully characterizes the Bauschinger effect, which is challenging to capture with a conventional continuum model without additional assumptions. The proposed model could be further employed in the design, manufacturing, and service of engineering components.