Sodium hypochlorite effects on dentin bond strength and acid-base resistant zone formation by adhesive systems

Aim: To evaluate the effects of 10% NaOCl gel application on the dentin bond strengths and morphology of resin-dentin interfaces formed by three adhesives. Methods: Two etch-and-rinse adhesives (One-Step Plus, Bisco Inc. and Clearfil Photo Bond, Kuraray Noritake Dental) and one self-etch adhesive (Clearfil SE Bond, Kuraray Noritake Dental) were applied on dentin according to the manufacturers’ instructions or after the treatment with 10% NaOCl (ED-Gel, Kuraray Noritake Dental) for 60 s. For interfacial analysis, specimens were subjected to acid-base challenge and observed by SEM to identify the formation of the acid-base resistant zone (ABRZ). For microtensile bond strength, the same groups were investigated and the restored teeth were thermocycled (5,000 cycles) or not before testing. Bond strength data were subjected to two-way ANOVA and Tukey’s test (p<0.05). Results: NaOCl application affected the bond strengths for One-Step Plus and Clearfil Photo Bond. Thermocycling reduced the bond strengths for Clearfil Photo Bond and Clearfil SE Bond when used after NaOCl application and One-Step Plus when used as recommended by manufacturer. ABRZ was observed adjacent to the hybrid layer for self-etch primer. The etch-and-rinse systems showed external lesions after acid-base challenge and no ABRZ formation when applied according to manufacturer’s instructions. Conclusions: 10% NaOCl changed the morphology of the bonding interfaces and its use with etch-&-rinse adhesives reduced the dentin bond strength. Formation of ABRZ was material-dependent and the interface morphologies were different among the tested materials.

Development and Verification of Control and Protection Strategies in Hybrid AC/DC Power Systems for Smart Grid Applications

Modern power networks incorporate communications and information technology infrastructure into the electrical power system to create a smart grid in terms of control and operation. The smart grid enables real-time communication and control between consumers and utility companies allowing suppliers to optimize energy usage based on price preference and system technical issues. The smart grid design aims to provide overall power system monitoring, create protection and control strategies to maintain system performance, stability and security. This dissertation contributed to the development of a unique and novel smart grid test-bed laboratory with integrated monitoring, protection and control systems. This test-bed was used as a platform to test the smart grid operational ideas developed here. The implementation of this system in the real-time software creates an environment for studying, implementing and verifying novel control and protection schemes developed in this dissertation. Phasor measurement techniques were developed using the available Data Acquisition (DAQ) devices in order to monitor all points in the power system in real time. This provides a practical view of system parameter changes, system abnormal conditions and its stability and security information system. These developments provide valuable measurements for technical power system operators in the energy control centers. Phasor Measurement technology is an excellent solution for improving system planning, operation and energy trading in addition to enabling advanced applications in Wide Area Monitoring, Protection and Control (WAMPAC). Moreover, a virtual protection system was developed and implemented in the smart grid laboratory with integrated functionality for wide area applications. Experiments and procedures were developed in the system in order to detect the system abnormal conditions and apply proper remedies to heal the system. A design for DC microgrid was developed to integrate it to the AC system with appropriate control capability. This system represents realistic hybrid AC/DC microgrids connectivity to the AC side to study the use of such architecture in system operation to help remedy system abnormal conditions. In addition, this dissertation explored the challenges and feasibility of the implementation of real-time system analysis features in order to monitor the system security and stability measures. These indices are measured experimentally during the operation of the developed hybrid AC/DC microgrids. Furthermore, a real-time optimal power flow system was implemented to optimally manage the power sharing between AC generators and DC side resources. A study relating to real-time energy management algorithm in hybrid microgrids was performed to evaluate the effects of using energy storage resources and their use in mitigating heavy load impacts on system stability and operational security.

Design Optimization of Modern Machine-drive Systems for Maximum Fault Tolerant and Optimal Operation

Modern electric machine drives, particularly three phase permanent magnet machine drive systems represent an indispensable part of high power density products. Such products include; hybrid electric vehicles, large propulsion systems, and automation products. Reliability and cost of these products are directly related to the reliability and cost of these systems. The compatibility of the electric machine and its drive system for optimal cost and operation has been a large challenge in industrial applications. The main objective of this dissertation is to find a design and control scheme for the best compromise between the reliability and optimality of the electric machine-drive system. The effort presented here is motivated by the need to find new techniques to connect the design and control of electric machines and drive systems. A highly accurate and computationally efficient modeling process was developed to monitor the magnetic, thermal, and electrical aspects of the electric machine in its operational environments. The modeling process was also utilized in the design process in form finite element based optimization process. It was also used in hardware in the loop finite element based optimization process. The modeling process was later employed in the design of a very accurate and highly efficient physics-based customized observers that are required for the fault diagnosis as well the sensorless rotor position estimation. Two test setups with different ratings and topologies were numerically and experimentally tested to verify the effectiveness of the proposed techniques. The modeling process was also employed in the real-time demagnetization control of the machine. Various real-time scenarios were successfully verified. It was shown that this process gives the potential to optimally redefine the assumptions in sizing the permanent magnets of the machine and DC bus voltage of the drive for the worst operating conditions. The mathematical development and stability criteria of the physics-based modeling of the machine, design optimization, and the physics-based fault diagnosis and the physics-based sensorless technique are described in detail. To investigate the performance of the developed design test-bed, software and hardware setups were constructed first. Several topologies of the permanent magnet machine were optimized inside the optimization test-bed. To investigate the performance of the developed sensorless control, a test-bed including a 0.25 (kW) surface mounted permanent magnet synchronous machine example was created. The verification of the proposed technique in a range from medium to very low speed, effectively show the intelligent design capability of the proposed system. Additionally, to investigate the performance of the developed fault diagnosis system, a test-bed including a 0.8 (kW) surface mounted permanent magnet synchronous machine example with trapezoidal back electromotive force was created. The results verify the use of the proposed technique under dynamic eccentricity, DC bus voltage variations, and harmonic loading condition make the system an ideal case for propulsion systems.

NEW DATA ON THE CHRONOLOGY OF THE VALE DO FORNO SEDIMENTARY SEQUENCE (LOWER TAGUS RIVER TERRACE STAIRCASE) AND ITS RELEVANCE AS FLUVIAL ARCHIVE OF THE MIDDLE PLEISTOCENE IN WESTERN IBERIA

NEW DATA ON THE CHRONOLOGY OF THE VALE DO FORNO SEDIMENTARY SEQUENCE (LOWER TAGUS RIVER TERRACE STAIRCASE) AND ITS RELEVANCE AS FLUVIAL ARCHIVE OF THE MIDDLE PLEISTOCENE IN WESTERN IBERIA Pedro P. Cunha 1, António A. Martins 2, Jan-Pieter Buylaert 3,4, Andrew S. Murray 4, Luis Raposo 5, Paolo Mozzi 6, Martin Stokes 7 1 MARE - Marine and Environmental Sciences Centre, Department of Earth Sciences, University of Coimbra, Portugal: pcunha@dct.uc.pt 2 MARE - Marine and Environmental Sciences Centre, Dep. Geociências, University of Évora, Portugal; aam@uevora.pt 3 Centre for Nuclear Technologies, Technical University of Denmark, Risø Campus, Denmark; jabu@dtu.dk 4 Nordic Laboratory for Luminescence Dating, Aarhus University, Risø DTU, Denmark; anmu@dtu.dk 5 Museu Nacional de Arqueologia, Lisboa, Portugal; 3raposos@sapo.pt 6 Department of Geosciences, University of Padova, Italy; paolo.mozzi@unipd.it 7 School of Geography, Earth and Environmental Sciences, University of Plymouth, UK; m.stokes@plymouth.ac.uk The stratigraphic units that record the evolution of the Tagus River in Portugal (study area between Vila Velha de Ródão and Porto Alto villages; Fig. 1) have different sedimentary characteristics and lithic industries (Cunha et al., 2012): - a culminant sedimentary unit (the ancestral Tagus, before the drainage network entrenchment) – SLD13 (+142 to 262 m above river bed – a.r.b.; with probable age ca. 3,6 to 1,8 Ma), without artefacts; - T1 terrace (+84 to 180 m; ca. 1000? to 900 ka), without artefacts; - T2 terrace (+57 to 150 m; top deposits with a probable age ca. 600 ka), without artefacts; - T3 terrace (+43 to 113 m; ca. 460 to 360? ka), without artefacts; - T4 terrace (+26 to 55 m; ca. 335 a 155 ka), Lower Paleolithic (Acheulian) at basal and middle levels but early Middle Paleolithic at top levels; - T5 terrace (+5 to 34 m; 135 to 73 ka), Middle Paleolithic (Mousterian; Levallois technique); - T6 terrace (+3 to 14 m; 62 to 32 ka), late Middle Paleolithic (late Mousterian); - Carregueira Sands (aeolian sands) and colluvium (+3 a ca. 100 m; 32 to 12 ka), Upper Paleolithic to Epipaleolithic; - alluvial plain (+0 to 8 m; ca. 12 ka to present), Mesolithic and more recent industries. The differences in elevation (a.r.b.) of the several terrace staircases results from differential uplift due to active faults. Longitudinal correlation with the terrace levels indicates that a graded profile ca. 200 km long was achieved during terrace formation periods and a strong control by sea base level was determinant for terrace formation. The Neogene sedimentary units constituted the main source of sediments for the fluvial terraces (Fig. 2). Geomorphological mapping, coupled with lithostratigraphy, sedimentology and luminescence dating (quartz-OSL and K-feldspar post-IRIR290) were used in this study focused on the T4 terrace, which comprises a Lower Gravels (LG) unit and an Upper Sand (US) unit. The thick, coarse and dominantly massive gravels of the LG unit indicate deposition by a coarse bed-load braided river, with strong sediment supply, high gradient and fluvial competence, during conditions of rapidly rising sea level. Luminescence dating only provided minimum ages but it is probable that the LG unit corresponds to the earlier part of the MIS9 (ca. 335 to 325 ka), immediately postdating the incision promoted by the very low sea level (reaching ca. -140 m) during MIS10 (362 to 337 ka), a period of relatively cold climate conditions with weak vegetation cover on slopes and low sea level. Fig. 1. Main Portuguese reaches in which the Tagus River can be divided (Lower Tagus Basin): I – from the Spanish border to Arneiro (a general E–W trend, mainly consisting of polygonal segments); II – from Arneiro to Gavião (NE–SW); III – from Gavião to Arripiado (E–W); IV – from Arripiado to Vila Franca de Xira (NNE-SSW); V – from Vila Franca de Xira to the Atlantic shoreline. The faults considered to be the limit of the referred fluvial sectors are: F1 – Ponsul-Arneiro fault (WSW-ENE); F2 – Gavião fault (NW-SE); F3 – Ortiga fault (NW-SE); F4 – Vila Nova da Barquinha fault (W-E); F5 – Arripiado-Chamusca fault (NNE-SSW). 1 – estuary; 2 – terraces; 3 – faults; 4 – Tagus main channel. The main Iberian drainage basins are also represented (inset). The lower and middle parts of the US unit, comprising an alternation of clayish silts with paleosols and minor sands to the east (flood-plain deposits) and sand deposits to the west (channel belt), have a probable age of ca. 325 to 200 ka. This points to formation during MIS9 to MIS7, under conditions of high to medium sea levels and warm to mild conditions. The upper part of the US unit, dominated by sand facies and with OSL ages of ca. 200 to 154 ka, correlates with the early part of the MIS6. During this period, progradation resulted from climate deterioration and relative depletion of vegetation that promoted enhanced sediment production in the catchment, coupled with initiation of sea-level lowering that increased the longitudinal slope. The Vale do Forno and Vale da Atela archaeological sites (Alpiarça, central Portugal) document the earliest human occupation in the Lower Tagus River, well established in geomorphological and environmental terms, within the Middle Pleistocene. The Lower Palaeolithic sites were found on the T4 terrace (+26 m, a.r.b.). The oldest artefacts previously found in the LG unit, display crude bifacial forms that can be attributed to the Acheulian, with a probable age of ca. 335 to 325 ka. The T4 US unit has archaeological sites stratigraphically documenting successive phases of an evolved Acheulian, that probably date ca. 325 to 300 ka. Notably, these Lower Palaeolithic artisans were able to produce tools with different sophistication levels, simply by applying different strategies: more elaborated reduction sequences in case of bifaces and simple reduction sequences to obtain cleavers. Fig. 2. . Simplified geologic map of the Lower Tagus Cenozoic basin, adapted from the Carta Geológica de Portugal, 1/500000, 1992). The study area (comprising the Vale do Forno and Vale de Atela sites) is located on the more upstream sector of the Lower Tagus River reach IV, between Arripiado and Chamusca villages. 1 – alluvium (Holocene); 2 – terraces (Pleistocene); 3 – sands, silts and gravels (Paleogene to Pliocene); 4 – Sintra Massif (Cretaceous); 5 – limestones, marls, silts and sandstones (Mesozoic); 6 – quartzites (Ordovician); 7 – basement (Proterozoic to Palaeozoic); 8 – main fault. The main Portuguese reaches of the Tagus River are identified (I to V). The VF3 site (Milharós), containing a Final Acheulian industry, with fine and elaborated bifaces) found in a stratigraphic level located between the T4 terrace deposits and a colluvium associated with Late Pleistocene aeolian sands (32 to 12 ka), has an age younger than ca. 154 ka but much older than 32 ka. In the study area, the sedimentary units of the T4 terrace seem to record the river response to sea-level changes and climatically-driven fluctuations in sediment supply. REFERENCES Cunha P. P., Almeida N. A. C., Aubry T., Martins A. A., Murray A. S., Buylaert J.-P., Sohbati R., Raposo L., Rocha L., 2012, Records of human occupation from Pleistocene river terrace and aeolian sediments in the Arneiro depression (Lower Tejo River, central eastern Portugal). Geomorphology, vol. 165-166, pp. 78-90.

AD-HOC principles of minimum energy expenditure as corollaries of the constructal law the cases of river basins and human vascular systems

In a recent paper [1] Reis showed that both the principles of extremum of entropy production rate, which are often used in the study of complex systems, are corollaries of the Constructal Law. In fact, both follow from the maximization of overall system conductivities, under appropriate constraints. In this way, the maximum rate of entropy production (MEP) occurs when all the forces in the system are kept constant. On the other hand, the minimum rate of entropy production (mEP) occurs when all the currents that cross the system are kept constant. In this paper it is shown how the so-called principle of "minimum energy expenditure" which is often used as the basis for explaining many morphologic features in biologic systems, and also in inanimate systems, is also a corollary of Bejan's Constructal Law [2]. Following the general proof some cases namely, the scaling laws of human vascular systems and river basins are discussed as illustrations from the side of life, and inanimate systems, respectively.

Robust Adaptive Control with Applications to Multi-Agent Systems and Mobile Robotics

This thesis deals with robust adaptive control and its applications, and it is divided into three main parts. The first part is about the design of robust estimation algorithms based on recursive least squares. First, we present an estimator for the frequencies of biased multi-harmonic signals, and then an algorithm for distributed estimation of an unknown parameter over a network of adaptive agents. In the second part of this thesis, we consider a cooperative control problem over uncertain networks of linear systems and Kuramoto systems, in which the agents have to track the reference generated by a leader exosystem. Since the reference signal is not available to each network node, novel distributed observers are designed so as to reconstruct the reference signal locally for each agent, and therefore decentralizing the problem. In the third and final part of this thesis, we consider robust estimation tasks for mobile robotics applications. In particular, we first consider the problem of slip estimation for agricultural tracked vehicles. Then, we consider a search and rescue application in which we need to drive an unmanned aerial vehicle as close as possible to the unknown (and to be estimated) position of a victim, who is buried under the snow after an avalanche event. In this thesis, robustness is intended as an input-to-state stability property of the proposed identifiers (sometimes referred to as adaptive laws), with respect to additive disturbances, and relative to a steady-state trajectory that is associated with a correct estimation of the unknown parameter to be found.

PCM-based battery thermal management systems, energy saving materials and LCA strategy for automotive

This PhD work arises from the necessity to give a contribution to the energy saving field, regarding automotive applications. The aim was to produce a multidisciplinary work to show how much important is to consider different aspects of an electric car realization: from innovative materials to cutting-edge battery thermal management systems (BTMSs), also dealing with the life cycle assessment (LCA) of the battery packs (BPs). Regarding the materials, it has been chosen to focus on carbon fiber composites as their use allows realizing light products with great mechanical properties. Processes and methods to produce carbon fiber goods have been analysed with a special attention on the university solar car Emilia 4. The work proceeds dealing with the common BTMSs on the market (air-cooled, cooling plates, heat pipes) and then it deepens some of the most innovative systems such as the PCM-based BTMSs after a previous experimental campaign to characterize the PCMs. After that, a complex experimental campaign regarding the PCM-based BTMSs has been carried on, considering both uninsulated and insulated systems. About the first category the tested systems have been pure PCM-based and copper-foam-loaded-PCM-based BTMSs; the insulated tested systems have been pure PCM-based and copper-foam-loaded-PCM-based BTMSs and both of these systems equipped with a liquid cooling circuit. The choice of lighter building materials and the optimization of the BTMS are strategies which helps in reducing the energy consumption, considering both the energy required by the car to move and the BP state of health (SOH). Focusing on this last factor, a clear explanation regarding the importance of taking care about the SOH is given by the analysis of a BP production energy consumption. This is why a final dissertation about the life cycle assessment (LCA) of a BP unit has been presented in this thesis.

Planning and flexible operation of storage systems in power grids: from transmission to distribution networks

The first part of the thesis has been devoted to the transmission planning with high penetration of renewable energy sources. Both stationary and transportable battery energy storage (BES, BEST) systems have been considered in the planning model, so to obtain the optimal set of BES, BEST and transmission lines that minimizes the total cost in a power network. First, a coordinated expansion planning model with fixed transportation cost for BEST devices has been presented; then, the model has been extended to a planning formulation with a distance-dependent transportation cost for the BEST units, and its tractability has been proved through a case study based on a 190-bus test system. The second part of this thesis is then devoted to the analysis of planning and management of renewable energy communities (RECs). Initially, the planning of photovoltaic and BES systems in a REC with an incentive-based remuneration scheme according to the Italian regulatory framework has been analysed, and two planning models, according to a single-stage, or a multi-stage approach, have been proposed in order to provide the optimal set of BES and PV systems allowing to achieve the minimum energy procurement cost in a given REC. Further, the second part of this thesis is devoted to the study of the day-ahead scheduling of resources in renewable energy communities, by considering two types of REC. The first one, which we will refer to as “cooperative community”, allows direct energy transactions between members of the REC; the second type of REC considered, which we shall refer to as “incentive-based”, does not allow direct transactions between members but includes economic revenues for the community shared energy, according to the Italian regulation framework. Moreover, dispatchable renewable energy generation has been considered by including producers equipped with biogas power plants in the community.

Modelling, simulations and monitoring for sustainable plant and animal production systems through precision technique

Protected crop production is a modern and innovative approach to cultivating plants in a controlled environment to optimize growth, yield, and quality. This method involves using structures such as greenhouses or tunnels to create a sheltered environment. These productive solutions are characterized by a careful regulation of variables like temperature, humidity, light, and ventilation, which collectively contribute to creating an optimal microclimate for plant growth. Heating, cooling, and ventilation systems are used to maintain optimal conditions for plant growth, regardless of external weather fluctuations. Protected crop production plays a crucial role in addressing challenges posed by climate variability, population growth, and food security. Similarly, animal husbandry involves providing adequate nutrition, housing, medical care and environmental conditions to ensure animal welfare. Then, sustainability is a critical consideration in all forms of agriculture, including protected crop and animal production. Sustainability in animal production refers to the practice of producing animal products in a way that minimizes negative impacts on the environment, promotes animal welfare, and ensures the long-term viability of the industry. Then, the research activities performed during the PhD can be inserted exactly in the field of Precision Agriculture and Livestock farming. Here the focus is on the computational fluid dynamic (CFD) approach and environmental assessment applied to improve yield, resource efficiency, environmental sustainability, and cost savings. It represents a significant shift from traditional farming methods to a more technology-driven, data-driven, and environmentally conscious approach to crop and animal production. On one side, CFD is powerful and precise techniques of computer modeling and simulation of airflows and thermo-hygrometric parameters, that has been applied to optimize the growth environment of crops and the efficiency of ventilation in pig barns. On the other side, the sustainability aspect has been investigated and researched in terms of Life Cycle Assessment analyses.

Self-etch Adhesive Systems: A Literature Review.

This paper presents the state of the art of self-etch adhesive systems. Four topics are shown in this review and included: the historic of this category of bonding agents, bonding mechanism, characteristics/properties and the formation of acid-base resistant zone at enamel/dentin-adhesive interfaces. Also, advantages regarding etch-and-rinse systems and classifications of self-etch adhesive systems according to the number of steps and acidity are addressed. Finally, issues like the potential durability and clinical importance are discussed. Self-etch adhesive systems are promising materials because they are easy to use, bond chemically to tooth structure and maintain the dentin hydroxyapatite, which is important for the durability of the bonding.

Unconventional neurotransmitters, neurodegeneration and neuroprotection

Neurotransmitters are also involved in functions other than conventional signal transfer between nerve cells, such as development, plasticity, neurodegeneration, and neuroprotection. For example, there is a considerable amount of data indicating developmental roles for the glutamatergic, cholinergic, dopaminergic, GABA-ergic, and ATP/adenosine systems. In this review, we discuss the existing literature on these "new" functions of neurotransmitters in relation to some unconventional neurotransmitters, such as the endocannabinoids and nitric oxide. Data indicating both transcriptional and post-transcriptional modulation of endocannabinoid and nitrinergic systems after neural lesions are discussed in relation to the non-conventional roles of these neurotransmitters. Knowledge of the roles of neurotransmitters in brain functions other than information transfer is critical for a more complete understanding of the functional organization of the brain and to provide more opportunities for the development of therapeutical tools aimed at minimizing neuronal death.

Revision of the species of the genus Cathorops (Siluriformes: Ariidae) from Mesoamerica and the Central American Caribbean, with description of three new species

The ariid genus Cathorops includes species that occur mainly in estuarine and freshwater habitats of the eastern and western coasts of southern Mexico, Central and South America. The species of Cathorops from the Mesoamerica (Atlantic slope) and Caribbean Central America are revised, and three new species are described: C. belizensis from mangrove areas in Belize; C. higuchii from shallow coastal areas and coastal rivers in the Central American Caribbean, from Honduras to Panama; and C. kailolae from río Usumacinta and lago Izabal basins in Mexico and Guatemala. Additionally, C. aguadulce, from the río Papaloapan basin in Mexico, and C. melanopus from the río Motagua basin in Guatemala and Honduras, are redescribed and their geographic distributions are revised.

Fossil groups in the Millennium simulation Their environment and its evolution

Context. Fossil systems are defined to be X- ray bright galaxy groups ( or clusters) with a two- magnitude difference between their two brightest galaxies within half the projected virial radius, and represent an interesting extreme of the population of galaxy agglomerations. However, the physical conditions and processes leading to their formation are still poorly constrained. Aims. We compare the outskirts of fossil systems with that of normal groups to understand whether environmental conditions play a significant role in their formation. We study the groups of galaxies in both, numerical simulations and observations. Methods. We use a variety of statistical tools including the spatial cross- correlation function and the local density parameter Delta(5) to probe differences in the density and structure of the environments of "" normal"" and "" fossil"" systems in the Millennium simulation. Results. We find that the number density of galaxies surrounding fossil systems evolves from greater than that observed around normal systems at z = 0.69, to lower than the normal systems by z = 0. Both fossil and normal systems exhibit an increment in their otherwise radially declining local density measure (Delta(5)) at distances of order 2.5 r(vir) from the system centre. We show that this increment is more noticeable for fossil systems than normal systems and demonstrate that this difference is linked to the earlier formation epoch of fossil groups. Despite the importance of the assembly time, we show that the environment is different for fossil and non- fossil systems with similar masses and formation times along their evolution. We also confirm that the physical characteristics identified in the Millennium simulation can also be detected in SDSS observations. Conclusions. Our results confirm the commonly held belief that fossil systems assembled earlier than normal systems but also show that the surroundings of fossil groups could be responsible for the formation of their large magnitude gap.

Spin gaps and spin-flip energies in density-functional theory

Energy gaps are crucial aspects of the electronic structure of finite and extended systems. Whereas much is known about how to define and calculate charge gaps in density-functional theory (DFT), and about the relation between these gaps and derivative discontinuities of the exchange-correlation functional, much less is known about spin gaps. In this paper we give density-functional definitions of spin-conserving gaps, spin-flip gaps and the spin stiffness in terms of many-body energies and in terms of single-particle (Kohn-Sham) energies. Our definitions are as analogous as possible to those commonly made in the charge case, but important differences between spin and charge gaps emerge already on the single-particle level because unlike the fundamental charge gap spin gaps involve excited-state energies. Kohn-Sham and many-body spin gaps are predicted to differ, and the difference is related to derivative discontinuities that are similar to, but distinct from, those usually considered in the case of charge gaps. Both ensemble DFT and time-dependent DFT (TDDFT) can be used to calculate these spin discontinuities from a suitable functional. We illustrate our findings by evaluating our definitions for the Lithium atom, for which we calculate spin gaps and spin discontinuities by making use of near-exact Kohn-Sham eigenvalues and, independently, from the single-pole approximation to TDDFT. The many-body corrections to the Kohn-Sham spin gaps are found to be negative, i.e., single-particle calculations tend to overestimate spin gaps while they underestimate charge gaps.

Self-organized distribution of periodicity and chaos in an electrochemical oscillator

We report a detailed numerical investigation of a prototype electrochemical oscillator, in terms of high-resolution phase diagrams for an experimentally relevant section of the control (parameter) space. The prototype model consists of a set of three autonomous ordinary differential equations which captures the general features of electrochemical oscillators characterized by a partially hidden negative differential resistance in an N-shaped current-voltage stationary curve. By computing Lyapunov exponents, we provide a detailed discrimination between chaotic and periodic phases of the electrochemical oscillator. Such phases reveal the existence of an intricate structure of domains of periodicity self-organized into a chaotic background. Shrimp-like periodic regions previously observed in other discrete and continuous systems were also observed here, which corroborate the universal nature of the occurrence of such structures. In addition, we have also found a structured period distribution within the order region. Finally we discuss the possible experimental realization of comparable phase diagrams.