Thermodynamic Response Research Articles

Understanding the Asian summer monsoon response to greenhouse warming: the relative roles of direct radiative forcing and sea surface temperature change

Future hydroclimate projections from state-of-the-art climate models show large uncertainty and model spread, particularly in the tropics and over the monsoon regions. The precipitation and circulation responses to rising greenhouse gases involve a fast component associated with direct radiative forcing and a slow component associated with sea surface temperature (SST) warming; the relative importance of the two may contribute to model discrepancies. In this study, regional hydroclimate responses to greenhouse warming are assessed using output from coupled general circulation models in the Coupled Model Intercomparison Project-Phase 5 (CMIP5) and idealized atmospheric general circulation model experiments from the Atmosphere Model Intercomparison Project. The thermodynamic and dynamic mechanisms causing the rainfall changes are examined using moisture budget analysis. Results show that direct radiative forcing and SST change exert significantly different responses both over land and ocean. For most part of the Asian monsoon region, the summertime rainfall changes are dominated by the direct CO2 radiative effect through enhanced monsoon circulation. The response to SST warming shows a larger model spread compared to direct radiative forcing, possibly due to the cancellation between the thermodynamical and dynamical components. While the thermodynamical response of the Asian monsoon is robust across the models, there is a lack of consensus for the dynamical response among the models and weak multi-model mean responses in the CMIP5 ensemble, which may be related to the multiple physical processes evolving on different time scales.

Modeling of soil nitrification responses to temperature reveals thermodynamic differences between ammonia-oxidizing activity of archaea and bacteria.

Soil nitrification potential (NP) activities of ammonia-oxidizing archaea and bacteria (AOA and AOB, respectively) were evaluated across a temperature gradient (4-42 °C) imposed upon eight soils from four different sites in Oregon and modeled with both the macromolecular rate theory and the square root growth models to quantify the thermodynamic responses. There were significant differences in response by the dominant AOA and AOB contributing to the NPs. The optimal temperatures (Topt) for AOA- and AOB-supported NPs were significantly different (P<0.001), with AOA having Topt>12 °C greater than AOB. The change in heat capacity associated with the temperature dependence of nitrification (ΔCP‡) was correlated with Topt across the eight soils, and the ΔCP‡ of AOB activity was significantly more negative than that of AOA activity (P<0.01). Model results predicted, and confirmatory experiments showed, a significantly lower minimum temperature (Tmin) and different, albeit very similar, maximum temperature (Tmax) values for AOB than for AOA activity. The results also suggested that there may be different forms of AOA AMO that are active over different temperature ranges with different Tmin, but no evidence of multiple Tmin values within the AOB. Fundamental differences in temperature-influenced properties of nitrification driven by AOA and AOB provides support for the idea that the biochemical processes associated with NH3 oxidation in AOA and AOB differ thermodynamically from each other, and that also might account for the difficulties encountered in attempting to model the response of nitrification to temperature change in soil environments.

Photovoltaic Devices: Opto-Electro-Thermal Physics and Modeling.

An opto-electro-thermal simulation of solar cells (SCs) is presented by addressing optoelectronic and thermodynamic responses simultaneously. The photocurrent losses due to carrier recombinations and the intrinsic heat generation (thermalization/Joule/Peltier/recombination heat) and dissipation (convective/radiative cooling) processes in the SCs are investigated quantitatively.

Nonequilibrium response of a voltage gated sodium ion channel and biophysical characterization of dynamic hysteresis

Here we have studied the dynamic as well as the non-equilibrium thermodynamic response properties of voltage-gated Na-ion channel. Using sinusoidally oscillating external voltage protocol we have both kinetically and energetically studied the non-equilibrium steady state properties of dynamic hysteresis in details. We have introduced a method of estimating the work done associated with the dynamic memory due to a cycle of oscillating voltage. We have quantitatively characterised the loop area of ionic current which gives information about the work done to sustain the dynamic memory only for ion conduction, while the loop area of total entropy production rate gives the estimate of work done for overall gating dynamics. The maximum dynamic memory of Na-channel not only depends on the frequency and amplitude but it also depends sensitively on the mean of the oscillating voltage and here we have shown how the system optimize the dynamic memory itself in the biophysical range of field parameters. The relation between the average ionic current with increasing frequency corresponds to the nature of the average dissipative work done at steady state. It is also important to understand that the utilization of the energy from the external field can not be directly obtained only from the measurement of ionic current but also requires nonequilibrium thermodynamic study.

Supercritical fluid of particles with a Yukawa potential: A new approximation for the direct correlation function and the Widom line

We propose an approximation of a direct correlation function corresponding to the linearization with respect to −βϕ(r) of a generalized mean spherical approximation for a hard-core multi-Yukawa system of particles. We use the results to study the behavior of maximums of thermodynamic response functions in the supercritical region of a fluid with a two-term Yukawa potential imitating the Lennard-Jones potential.

Thermodynamic and Kinetic Response of Microbial Reactions to High CO2.

Geological carbon sequestration captures CO2 from industrial sources and stores the CO2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO2 concentration. This study uses biogeochemical modeling to explore the influence of CO2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses.

Thermodynamics of Noncommutative Quantum Kerr Black Holes

The thermodynamic formalism for rotating black holes, characterized by noncommutative and quantum corrections, is constructed. From a fundamental thermodynamic relation, the equations of state and thermodynamic response functions are explicitly given, and the effect of noncommutativity and quantum correction is discussed. It is shown that the well-known divergence exhibited in specific heat is not removed by any of these corrections. However, regions of thermodynamic stability are affected by noncommutativity, increasing the available states for which some thermodynamic stability conditions are satisfied.

Exact Diagonalization Study of an Extended Hubbard Model for a Cubic Cluster at Quarter Filling

In the paper the thermodynamics of a cubic cluster with 8 sites at quarter filling is characterized by means of exact diagonalization technique. Particular emphasis is put on the behaviour of such response functions as specific heat and magnetic susceptibility. The system is modelled with extended Hubbard model which includes electron hopping between both first and second nearest neighbours as well as coulombic interactions, both on-site and between nearest-neighbour sites. The importance of hopping between second nearest neighbours and coulombic interactions between nearest neighbours for the temperature dependences of thermodynamic response functions is analysed. In particular, the predictions of Schottky model are compared with the calculations based on the full energy spectrum.

The structural validity of various thermodynamical models of supercooled water

The thermodynamic response functions of water exhibit an anomalous increase upon cooling that becomes strongly amplified in the deeply supercooled regime due to structural fluctuations between disordered and tetrahedral local structures. Here, we compare structural data from recent x-ray laser scattering measurements of water at 1 bar and temperatures down to 227 K with structural properties computed for several different water models using molecular dynamics simulations. Based on this comparison, we critically evaluate four different thermodynamic scenarios that have been invoked to explain the unusual behavior of water. The critical point-free model predicts small variations in the tetrahedrality with decreasing temperature, followed by a stepwise change at the liquid-liquid transition around 228 K at ambient pressure. This scenario is not consistent with the experimental data that instead show a smooth and accelerated variation in structure from 320 to 227 K. Both the singularity-free model and ice coarsening hypothesis give trends that indirectly indicate an increase in tetrahedral structure with temperature that is too weak to be consistent with experiment. A model that includes an apparent divergent point (ADP) at high positive pressure, however, predicts structural development consistent with our experimental measurements. The terminology ADP, instead of the commonly used liquid-liquid critical point, is more general in that it focuses on the growing fluctuations, whether or not they result in true criticality. Extrapolating this model beyond the experimental data, we estimate that an ADP in real water may lie around 1500 ± 250 bars and 190 ± 6 K.

Identification and modeling of geochemical reactions occurring within the sandstone reservoir flooded by seawater

Field X has one of the harshest oilfield scaling regimes in the North Sea and frequent squeeze treatments were implemented, so it will be beneficial to study and identify reservoir interactions among formation water, injected seawater, and reservoir rock, and even predict or evaluate scale problems in the field. For this field, produced water is sampled repeatedly during production and observation and analyses of variations in produced water chemical composition could reveal the extent of brine mixing in the field and enables an in-depth understanding of the fluid-fluid/fluid-rock interactions occurring in the reservoir during water injection. Produced water chemical compositional data from one well have been presented to provide a basic understanding of what geochemical reactions were possibly occurring in the reservoir, which could be then verified through developing a one-dimensional reactive transport model. Any possible occurring reactions among minerals, mixture of formation water and seawater, and CO2 gas phase would be included in this model to study their effects on variation in produced water chemical composition. A fairly good match between modelled and observed produced water chemical composition has been achieved through varying solubility products and the initial amount of some minerals, ion exchange capacity, and CO2 partial pressure, which indicates that the final achieved model, could, to some extent, reveal the physical, chemical, and thermodynamic responses of this reservoir system to injected seawater.

Tunable Negative Thermal Expansion in Layered Perovskites from Quasi-Two-Dimensional Vibrations.

We identify a quasi-two-dimensional (quasi-2D) phonon mode in the layered-perovskite Ca_{3}Ti_{2}O_{7}, which exhibits an acoustic branch with quadratic dispersion. Using first-principles methods, we show this mode exhibits atomic displacements perpendicular to the layered [CaTiO_{3}]_{2} blocks comprising the structure and a negative Grüneisen parameter. Owing to these quasi-2D structural and dynamical features, we find that the mode can be utilized to realize unusual membrane effects, including a tunable negative thermal expansion (NTE) and a rare pressure-independent thermal softening of the bulk modulus. Detailed microscopic analysis shows that the NTE relies on strong intralayer Ti-O covalent bonding and weaker interlayer interactions, which is in contrast to conventional NTE mechanisms for perovskites, such as rigid-unit modes, structural transitions, and electronic or magnetic ordering. The general application of the quasi-2D lattice dynamics opens exciting avenues for the control of lattice dynamical and thermodynamic responses of other complex layered compounds through rational chemical substitution, as we show in A_{3}Zr_{2}O_{7} (A=Ca, Sr), and by heterostructuring.

Finite Element Algorithm for Dynamic Thermoelasticity Coupling Problems and Application to Transient Response of Structure with Strong Aerothermodynamic Environment

AbstractAs an exploratory study for structural deformation and thermodynamic response induced by spacecraft reentry aerodynamic force and thermal environment, a finite element algorithm is presented on the basis of the classic Fourier heat conductive law to simulate the dynamic thermoelasticity coupling performance of the material. The Newmark method and Crank-Nicolson scheme are utilized to discretize the dynamic thermoelasticity equation and heat conductive equation in the time domain, respectively, and the unconditionally stable implicit algorithm is constructed. Four types of finite-element computing schemes are devised and discussed to solve the thermodynamic coupling equation, all of which are implemented and compared in the computational examples including the one-dimensional transient heat conduction in considering and not considering the vibration, the transient heat flow for the infinite cylinder, and the dynamic coupling thermoelasticity around re-entry flat plate from hypersonic aerothermodynamic environment. The computational results show that the transient responses of temperature and displacement field generate lag phenomenon in case of considering the deformation effect on temperature field. Propagation, rebounding, attenuation and stabilized phenomena of elastic wave are also observed by the finite-element calculation of thermodynamic coupling problem considering vibration and damping, and the oscillation of the temperature field is simultaneously induced. As a result, the computational method and its application research platform have been founded to solve the transient thermodynamic coupling response problem of the structure in strong aerodynamic heating and force environment. By comparing various coupling calculations, it is demonstrated that the present algorithm could give a correct and reliable description of transient thermodynamic responses of structure, the rationality of the sequentially coupling method in engineering calculation is discussed, and the bending deformation mechanism produced by the thermodynamic coupling response from windward and leeward sides of flying body is revealed, which lays the foundation in developing the numerical method to solve material internal temperature distribution, structural deformation, and thermal damage induced by spacecraft dynamic thermoelasticity coupling response under uncontrolled reentry aerothermodynamic condition.

Anomalous properties and the liquid-liquid phase transition in gallium.

A group of materials including water and silicon exhibit many anomalous behaviors, e.g., density anomaly and diffusivity anomaly (increase upon compression). These materials are hypothesized to have a liquid-liquid phase transition (LLPT) and the critical fluctuation in the vicinity of the liquid-liquid critical point is considered as the origin of different anomalies. Liquid gallium was also reported to have a LLPT, yet whether it shows similar water-like anomalies is not yet studied. Using molecular dynamics simulations on a modified embedded-atom model, we study the thermodynamic, dynamic, and structural properties of liquid gallium as well as its LLPT. We find that, similar to water-like materials predicted to have the LLPT, gallium also shows different anomalous behaviors (e.g., density anomaly, diffusivity anomaly, and structural anomaly). We also find that its thermodynamic and structural response functions are continuous and show maxima in the supercritical region, the loci of which asymptotically approach to the other and merge to the Widom line. These phenomena are consistent with the supercritical phenomenon in a category of materials with a liquid-liquid critical point, which could be common features in most materials with a LLPT.

Complete equation of state for shocked liquid nitrogen: Analytical developments.

The thermodynamic response of liquid nitrogen has been studied extensively, in part, due to the long-standing interest in the high pressure and high temperature dissociation of shocked molecular nitrogen. Previous equation of state (EOS) developments regarding shocked liquid nitrogen have focused mainly on the use of intermolecular pair potentials in atomistic calculations. Here, we present EOS developments for liquid nitrogen, incorporating analytical models, for use in continuum calculations of the shock compression response. The analytical models, together with available Hugoniot data, were used to extrapolate a low pressure reference EOS for molecular nitrogen [R. Span et al., J. Phys. Chem. Ref. Data 29, 1361 (2000)] to high pressures and high temperatures. Using the EOS presented here, the calculated pressures and temperatures for single shock, double shock, and multiple shock compression of liquid nitrogen provide a good match to the measured results over a broad range of P-T space. These calculations provide the first comparison of EOS developments with recently measured P-T states under multiple shock compression. The present EOS developments are general and are expected to be useful for other liquids that have low pressure reference EOS information available.

Attributing human mortality during extreme heat waves to anthropogenic climate change

It has been argued that climate change is the biggest global health threat of the 21st century. The extreme high temperatures of the summer of 2003 were associated with up to seventy thousand excess deaths across Europe. Previous studies have attributed the meteorological event to the human influence on climate, or examined the role of heat waves on human health. Here, for the first time, we explicitly quantify the role of human activity on climate and heat-related mortality in an event attribution framework, analysing both the Europe-wide temperature response in 2003, and localised responses over London and Paris. Using publicly-donated computing, we perform many thousands of climate simulations of a high-resolution regional climate model. This allows generation of a comprehensive statistical description of the 2003 event and the role of human influence within it, using the results as input to a health impact assessment model of human mortality. We find large-scale dynamical modes of atmospheric variability remain largely unchanged under anthropogenic climate change, and hence the direct thermodynamical response is mainly responsible for the increased mortality. In summer 2003, anthropogenic climate change increased the risk of heat-related mortality in Central Paris by ∼70% and by ∼20% in London, which experienced lower extreme heat. Out of the estimated ∼315 and ∼735 summer deaths attributed to the heatwave event in Greater London and Central Paris, respectively, 64 (±3) deaths were attributable to anthropogenic climate change in London, and 506 (±51) in Paris. Such an ability to robustly attribute specific damages to anthropogenic drivers of increased extreme heat can inform societal responses to, and responsibilities for, climate change.

Numerical Model to Quantify the Influence of the Cellulosic Substrate on the Ignition Propensity Tests

SUMMARY A numerical model based on the finite element method has been constructed to simulate the ignition propensity (IP) tests. The objective of this mathematical model was to quantify the influence of different characteristics of the cellulosic substrate on the results of the IP-tests. The creation and validation of the model included the following steps: (I) formulation of the model based on experimental thermodynamic characteristics of the cellulosic substrate; (ii) calibration of the model according to cone calorimeter tests; (iii) validation of the model through mass loss and temperature profiling during IP-testing. Once the model was validated, the influence of each isolated parameter of the cellulosic substrate was quantified via a parametric study. The results revealed that the substrate heat capacity, the cigarette temperature and the pyrolysis activation energy are the most influencing parameters on the thermodynamic response of the substrates, while other parameters like heat of the pyrolysis reaction, density and roughness of the substrate showed little influence. Also the results indicated that the thermodynamic mechanisms involved in the pyrolysis and combustion of the cellulosic substrate are complex and show low repeatability which might impair the reliability of the IP-tests.

Material Based Structure Design: Numerical Analysis Thermodynamic Response of Thermal Pyrolytic Graphite /Al Sandwich Composites

Amine-grafted multiwalled carbon nanotubes (MWCNTs) based thermally conductive adhesive (TCA) was studied in the previous paper and applied here in thermal pyrolytic graphite (TPG)/Al radiator due to its high thermal conductivity, toughness and cohesiveness. In this paper, in an attempt to confirm the application of TCA to TPG/Al sandwich radiator, the thermodynamic response in TPG/Al sandwich composites associated with key material properties and structural design was investigated using finite element simulation with commercial available ANSYS software. The induced thermal stress in TCA layer is substantial due to the thermal expansion mismatch between Al plate and TPG. The maximum thermal stress is located near the edge of TCA layer with the von Mises stress value of 4.02 MPa and the shear stress value of 1.66 MPa. The reasonable adjustment of physical-mechanical properties including thermal conductivity, thermal expansion, Young,s modulus and the thickness of TCA layer, Al plate and TPG are beneficial for reducing the temperature of the top surface of the upper skin and their effects on the reduction of thermal structural response in some ways. These findings will highlight the structural optimization of TPG/Al radiator for future application.

Relationship between the line of density anomaly and the lines of melting, crystallization, cavitation, and liquid spinodal in coarse-grained water models.

Liquid water has several anomalous properties, including a non-monotonous dependence of density with temperature and an increase of thermodynamic response functions upon supercooling. Four thermodynamic scenarios have been proposed to explain the anomalies of water, but it is not yet possible to decide between them from experiments because of the crystallization and cavitation of metastable liquid water. Molecular simulations provide a versatile tool to study the anomalies and phase behavior of water, assess their agreement with the phenomenology of water under conditions accessible to experiments, and provide insight into the behavior of water in regions that are challenging to probe in the laboratory. Here we investigate the behavior of the computationally efficient monatomic water models mW and mTIP4P/2005(REM), with the aim of unraveling the relationships between the lines of density extrema in the p-T plane, and the lines of melting, liquid-vapor spinodal and non-equilibrium crystallization and cavitation. We focus particularly on the conditions for which the line of density maxima (LDM) in the liquid emerges and disappears as the pressure is increased. We find that these models present a retracing LDM, same as previously found for atomistic water models and models of other tetrahedral liquids. The low-pressure end of the LDM occurs near the pressure of maximum of the melting line, a feature that seems to be general to models that produce tetrahedrally coordinated crystals. We find that the mW water model qualitatively reproduces several key properties of real water: (i) the LDM is terminated by cavitation at low pressures and by crystallization of ice Ih at high pressures, (ii) the LDM meets the crystallization line close to the crossover in crystallization from ice Ih to a non-tetrahedral four-coordinated crystal, and (iii) the density of the liquid at the crossover in crystallization from ice Ih to a four-coordinated non-tetrahedral crystal coincides with the locus of maximum in diffusivity as a function of pressure. The similarities in equilibrium and non-equilibrium phase behavior between the mW model and real water provide support to the quest to find a compressibility extremum, and determine whether it presents a maximum, in the doubly metastable region.

Engineering and characterization of fluorogenic glycine riboswitches

A set of 12 fluorogenic glycine riboswitches with different thermodynamic and kinetic response properties was engineered. For the design of functional riboswitches, a three-part RNA approach was applied based on the idea of linking a RNA sensor, transmitter and actuator part together. For the RNA sensor and actuator part, we used the tandem glycine aptamer structure from Bacillus subtillis, and fluorogenic aptamer Spinach, respectively. To achieve optimal signal transduction from the sensor to the actuator, a riboswitch library with variable transmitter was screened with a microfluidic large-scale integration chip. This allowed us to establish the complete thermodynamic binding profiles of the riboswitch library. Glycine dissociation constants of the 12 strong fluorescence response riboswitches varied between 99.7 and 570 μM. Furthermore, the kinetic glycine binding (kon), and dissociation (koff) rates, and corresponding energy barriers of the 10 strongest fluorescence response riboswitches were determined with the same chip platform. kon and koff were in the order of 10−3s−1 and 10−2s−1, respectively. Conclusively, we demonstrate that systematic screening of synthetic and natural linked RNA parts with microfluidic chip technology is an effective approach to rapidly generate fluorogenic metabolite riboswitches with a broad range of biophysical response properties.

Going beyond the BCS level in the superfluid path integral: A consistent treatment of electrodynamics and thermodynamics

In this paper we show how to redress a shortcoming of the path integral scheme for fermionic superfluids and superconductors. This approach is built around a simultaneous calculation of electrodynamics and thermodynamics. An important sum rule, the compressibility sum rule, fails to be satisfied in the usual calculation of the electromagnetic and thermodynamic response at the Gaussian fluctuation level. Here we present a path integral scheme to address this inconsistency. Specifically, at the leading order we argue that the superconducting gap should be calculated using a different saddle point condition modified by the presence of an external vector potential. This leads to the well known gauge-invariant BCS electrodynamic response and is associated with the usual (mean field) expression for thermodynamics. In this way the compressibility sum rule is satisfied at the BCS level. Moreover, this scheme can be readily extended to address arbitrary higher order fluctuation theories. At any level this approach will lead to a gauge invariant and compressibility sum rule consistent treatment of electrodynamics and thermodynamics.