Detailed electron paramagnetic resonance and electron nuclear double resonance experiments on the co-crystalline complex of 1-methylthymine:9-methyladenine (MTMA) have revealed that the major radiation induced products at low temperatures (10 K) are MTMA1, a radical formed by net hydrogen abstraction from the C5 methyl group on thymine, and MTMA2, a radical formed by net hydrogen abstraction of the N1 methyl group on thymine. The following four minor products were also observed: MTMA3, the C4-OH protonated anion of thymine, MTMA4, the C6 H-addition product of thymine, and MTMA5 and MTMA6, radicals formed by net H-addition to C2 and C8 of the adenine base. The geometries, energetics and hyperfine properties of all possible radicals of MT and MA, the primary anions and cations, as well as radicals formed via net hydrogen atom abstraction (deprotonated cations) or addition (protonated anions) were investigated theoretically. All systems were optimized using the hybrid Hartree-Fock density functional theory functional B3LYP, in conjunction with the 6-31G(d,p) basis set of Pople and co-workers. Calculations of the anisotropic hyperfine couplings for all the radicals observed in MTMA are presented, and are shown to compare favorably with the experimentally measured hyperfine couplings. The calculated ionizations potentials indicate that MA would be the preferred oxidation site. However, in MTMA neither the adenine cation nor its N4-deprotonated derivative were observed. The adenine cation in MTMA is not stabilized by deprotonation, and is thus likely subject to recombination. The calculated electron affinities indicate that MT would be the preferred reduction site. Reduction of MT is believed to result in protonation of the anion at C4=O. The calculated hyperfine couplings for the MT anion are very similar to those of the C4-OH protonated anion, and therefore, the theoretical calculations are not useful in deciding the actual protonation state of this reduction product.

<p>The increased use of biomass and recovered waste fuels in favor of fossil fuels for heat and power production is an important step towards a sustainable future. Combustion of waste fuels also offers several advantages over traditional landfilling, such as substantial volume reduction, detoxification of pathological wastes, and reduction of toxic leaches and greenhouse gas (methane) formation from landfills. However, combustion of recovered waste fuels emits more harmful trace elements than combustion of other fuels. These elements are distributed between bottom ash, fly ash and flue gas, depending on the elements partitioning and enrichment behavior. Volatilized harmful trace elements are mainly enriched in the submicron fly ash fraction. If emitted to the atmosphere, submicron particles can penetrate deep into the alveoli of the lungs, causing severe impacts on human health. Consequently, to reduce ash related problems and to control the emissions to the atmosphere, there is an increased need for understanding the physicochemical processes involved in ash transformation, including particle formation.</p><p>The objective of this thesis was to carefully and systematically study the fate of trace elements during combustion, i.e. the chemical form of the elements and the partitioning behavior, by means of chemical equilibrium model calculations, X-ray diffraction, microscopy techniques and various spectroscopy methods. The influence of some fuel additives was also analyzed. Primarily, the elements copper, chromium and arsenic were studied.</p><p>An initial review and evaluation of the content of thermodynamical data in commercial thermochemical databases used for chemical equilibrium model calculations showed that there was a significant difference in number of included phases and species between databases. Thermodynamical data also differed between databases, although in general less for condensed phases than for gaseous species. A state-of-the-art database for Cu, Cr and As was compiled and used for further chemical equilibrium model calculations. The fate of Cu, Cr and As was determined in combustion experiments on wood impregnated with copper, chromium and arsenic (CCA) in a bench scale reactor (15 kW). The results showed that global chemical equilibrium model calculations predicted the overall fate of Cu, Cr and As in bottom ash and ash particles quite well. However, compared to the experimental results the global model overpredicted the formation of refractory calcium arsenates, thus the arsenic volatilization was found to be higher then the predicted volatilization. In terms of chromium volatility, copper was found to be an important refractory element forming stable CuCrO₂(s) and CuCr₂O₄(s) that suppressed the formation of CrO₂(OH)₂(g). The retention and speciation of Cu, Cr and As in bottom ash was further determined from combustion experiments of CCA wood fuel particles in a single particle reactor. Local chemical equilibrium model calculations were performed to simulate the combustion stages of a burning CCA treated wood fuel particle: drying, devolatilization, char burning and post-combustion. The results from the work showed that a mix of global and local chemical equilibrium model calculations is needed to describe the reality and that the combustion stages are partially overlapping. The fate of harmful trace elements, including Cu, Cr and As, was finally studied in full scale (65 MW) combustion experiments. Particles from the raw flue gas emissions were sampled and analyzed. The comparison with chemical equilibrium model calculations showed that the model explained the results well, but due to lack of thermodynamic data for K₂ZnCl₄(s), the formation of this phase could not be predicted.</p>

The increased use of biomass and recovered waste fuels in favor of fossil fuels for heat and power production is an important step towards a sustainable future. Combustion of waste fuels also offers several advantages over traditional landfilling, such as substantial volume reduction, detoxification of pathological wastes, and reduction of toxic leaches and greenhouse gas (methane) formation from landfills. However, combustion of recovered waste fuels emits more harmful trace elements than combustion of other fuels. These elements are distributed between bottom ash, fly ash and flue gas, depending on the elements partitioning and enrichment behavior. Volatilized harmful trace elements are mainly enriched in the submicron fly ash fraction. If emitted to the atmosphere, submicron particles can penetrate deep into the alveoli of the lungs, causing severe impacts on human health. Consequently, to reduce ash related problems and to control the emissions to the atmosphere, there is an increased need for understanding the physicochemical processes involved in ash transformation, including particle formation. The objective of this thesis was to carefully and systematically study the fate of trace elements during combustion, i.e. the chemical form of the elements and the partitioning behavior, by means of chemical equilibrium model calculations, X-ray diffraction, microscopy techniques and various spectroscopy methods. The influence of some fuel additives was also analyzed. Primarily, the elements copper, chromium and arsenic were studied. An initial review and evaluation of the content of thermodynamical data in commercial thermochemical databases used for chemical equilibrium model calculations showed that there was a significant difference in number of included phases and species between databases. Thermodynamical data also differed between databases, although in general less for condensed phases than for gaseous species. A state-of-the-art database for Cu, Cr and As was compiled and used for further chemical equilibrium model calculations. The fate of Cu, Cr and As was determined in combustion experiments on wood impregnated with copper, chromium and arsenic (CCA) in a bench scale reactor (15 kW). The results showed that global chemical equilibrium model calculations predicted the overall fate of Cu, Cr and As in bottom ash and ash particles quite well. However, compared to the experimental results the global model overpredicted the formation of refractory calcium arsenates, thus the arsenic volatilization was found to be higher then the predicted volatilization. In terms of chromium volatility, copper was found to be an important refractory element forming stable CuCrO2(s) and CuCr2O4(s) that suppressed the formation of CrO2(OH)2(g). The retention and speciation of Cu, Cr and As in bottom ash was further determined from combustion experiments of CCA wood fuel particles in a single particle reactor. Local chemical equilibrium model calculations were performed to simulate the combustion stages of a burning CCA treated wood fuel particle: drying, devolatilization, char burning and post-combustion. The results from the work showed that a mix of global and local chemical equilibrium model calculations is needed to describe the reality and that the combustion stages are partially overlapping. The fate of harmful trace elements, including Cu, Cr and As, was finally studied in full scale (65 MW) combustion experiments. Particles from the raw flue gas emissions were sampled and analyzed. The comparison with chemical equilibrium model calculations showed that the model explained the results well, but due to lack of thermodynamic data for K2ZnCl4(s), the formation of this phase could not be predicted.

<p>Fosfaters reaktioner i energiomvandlingsprocesser är kritisk för den generella processen som helhet, för askrelaterade problem, emissioner liksom för en effektiv och hållbar användning av askan.</p><p>Denna avhandling är en sammanställning och diskussion med utgångspunkt i åtta artiklar som behandlar strukturella och termodynamiska studier på faser i CaO-K₂O-P₂O₅-systemet, vilka är av relevans inom förbränning av biomassa. Målsättningen med denna avhandling var: i) att sammanställa och granska tillgängliga strukturella och termodynamiska data i CaO-K₂O-P₂O₅-systemet samt att identifiera avsaknad av data, ii) att fylla i dessa luckor med grundläggande termodynamiska, strukturella och fasstabilitets studier samt iii) att visa på användning samt fördelarna med dessa nya data vid praktisk tillämpning.</p><p>En initial litteraturundersökning i CaO-K₂O-P₂O₅-systemet visade att det saknades både strukturella och termodynamiska data. När det gällde tillgängliga termodynamiska data var situationen särskilt otillfredsställande. Det fanns endast data för några kalcium– och kaliumfosfater med varierande tillförlitlighet. Situationen beträffande pulverröntgen för fasidentifiering var bättre, fast fördunklad av det faktum att strukturellt liknande fasövergångar ofta förekommer i det undersökta systemet. Däremot fattades det tillfredställande enkristallstrukturdata för ternära faser i det undersökta systemet.</p><p>Enkristallröntgendiffraktion användes för att bestämma strukturerna för CaK₂P₂O₇, CaKP₃O₉, Ca₁₀K(PO₄)₇ och CaKPO₄. Faserna CaK₂P₂O₇ and CaKPO₄ tillsammans med Ca₃(PO₄)₂, KPO₃ och K₄P₂O₇ studerades med pulverröntgendiffraktion och termiska analysmetoder för att klargöra fasmodifikationer och övergångstemperaturer. Gibbs bildningsenergi bestämdes för Ca(PO₃)₂, Ca₂P₂O₇, Ca₃(PO₄)₂, Ca₁₀K(PO₄)₇, CaK₂P₂O₇, CaKPO₄ och CaK₄(PO₄)₂ med ems-metodik och yttriastabiliserad zirkonia som fast elektrolyt och Ni/Ni₃P som hjälpsystem. Både de strukturella och termodynamiska data användes sedan vid analyser i ett förbrännningexperiment av olika sädesslag. Framtagna data användes både vid identifiering och även vid kvantifiering av bildade faser i biomassaresterna.</p> / <p>The behaviour of phosphates in thermochemical biomass conversion processes are critical for the general process chemistry, for ash related problems, for emissions as well as for an efficient, sustainable and beneficial use of the ash residues.</p><p>This thesis is a summary and a discussion of eight papers dealing with structural and thermodynamical studies of phases in the CaO-K₂O-P₂O₅ system, with relevance for biomass combustion. The objectives were: i) to compile and review the available structural and thermodynamical data of phases in the CaO-K₂O-P₂O₅ system as well as to identify existing gaps in the field of these data, ii) to fill in as many as possible of the gaps by fundamental thermodynamic, structural and phase stability studies and iii) to demonstrate the uses and the benefits of the new data in practical applications.</p><p>An initial review of the CaO-K₂O-P₂O₅ system showed that both structural information and thermodynamic data were lacking. The situation regarding the available thermodynamic data was especially unsatisfactory, data could only be found for some few calcium phosphates and a few potassium phosphates with varying reliability. Concerning powder X-ray diffraction patterns for phase identification the situation was better, though obscured by the fact that structurally close related phase transitions often occur in the studied system. However, adequate single crystal structural data of ternary phases in the system was completely missing.</p><p>Crystal structures of CaK₂P₂O₇, CaKP₃O₉, Ca₁₀K(PO₄)₇ and CaKPO₄ were determined by single-crystal X-ray diffraction. The phases CaK₂P₂O₇ and CaKPO₄ were together with Ca₃(PO₄)₂, KPO₃ and K₄P₂O₇, investigated by powder X-ray diffraction and thermal analysis to elucidate phase modifications and transitions temperatures. Gibbs standard energy of formation was determined for Ca(PO₃)₂, Ca₂P₂O₇, Ca₃(PO₄)₂, Ca₁₀K(PO₄)₇, CaK₂P₂O₇, CaKPO₄ and CaK₄(PO₄)₂ by solid state emf measurements with yttria stabilised zirconia as solid electrolyte and Ni/Ni₃P as auxiliary solid couple. Both the structural and thermodynamical data were subsequently utilised in analysis of a combustion experiment of cereal grains. The data were also used to both identify and quantify the phases formed in biomass combustion residues.</p>

<p>This thesis addresses the electronic structure of vanadium and copper oxides using soft X-ray absorption (SXA) spectroscopy and resonant inelastic X-ray scattering (RIXS) at high brightness synchrotron radiation sources. In RIXS incident photons, tuned to the energy of specific absorption resonances, are inelastically scattered leaving behind a low energy valence excitation in the system studied. Effects of electron localization are reflected by the occurrence of low-energy excitations in form of dd- and charge-transfer excitations that are modelled by cluster calculations. Band-like states are dominating when the intermediate core excited state is delocalized.</p><p>RIXS at V 2p and O 1s resonances has been used to study the electronic structure of the monovalent vanadium oxides VO₂ and V₂O₃, and of the mixed valence compounds, NaV₂O₅ and V₆O₁₃. For NaV₂O₅ and V₆O₁₃ significant contributions from localized low-energy excitations reflect the partly localized character of their valence band electronic structure, whereas VO₂ and V₂O₃ appear mostly as band-like. Effects of carrier doping are addressed for the case of Mo doping into VO₂ and reveal a quasi-rigid band behavior. In the cases of VO₂ and V₆O₁₃ the temperature dependent metal-insulator transition could be monitored by following the spectral evolution of bands originating from V 3d and V 3d - O2p hybridized states. For Na₂V₃O₇ nanotubes it was possible to selectively probe states from the apical and the basal oxygen sites of VO₅ pyramids that constitute these nanotubes. Furthermore, the RIXS technique has been demonstrated to be highly valuable in characterizing the charge transfer processes that accompany lithium insertion into vanadium oxide battery cathodes. Finally, for insulating cuprates RIXS at O 1s, Cu 3p and Cu 3s resonances has been recorded at high-resolution for the detailed investigation of crystal field excitations.</p>

This thesis addresses the electronic structure of vanadium and copper oxides using soft X-ray absorption (SXA) spectroscopy and resonant inelastic X-ray scattering (RIXS) at high brightness synchrotron radiation sources. In RIXS incident photons, tuned to the energy of specific absorption resonances, are inelastically scattered leaving behind a low energy valence excitation in the system studied. Effects of electron localization are reflected by the occurrence of low-energy excitations in form of dd- and charge-transfer excitations that are modelled by cluster calculations. Band-like states are dominating when the intermediate core excited state is delocalized. RIXS at V 2p and O 1s resonances has been used to study the electronic structure of the monovalent vanadium oxides VO2 and V2O3, and of the mixed valence compounds, NaV2O5 and V6O13. For NaV2O5 and V6O13 significant contributions from localized low-energy excitations reflect the partly localized character of their valence band electronic structure, whereas VO2 and V2O3 appear mostly as band-like. Effects of carrier doping are addressed for the case of Mo doping into VO2 and reveal a quasi-rigid band behavior. In the cases of VO2 and V6O13 the temperature dependent metal-insulator transition could be monitored by following the spectral evolution of bands originating from V 3d and V 3d - O2p hybridized states. For Na2V3O7 nanotubes it was possible to selectively probe states from the apical and the basal oxygen sites of VO5 pyramids that constitute these nanotubes. Furthermore, the RIXS technique has been demonstrated to be highly valuable in characterizing the charge transfer processes that accompany lithium insertion into vanadium oxide battery cathodes. Finally, for insulating cuprates RIXS at O 1s, Cu 3p and Cu 3s resonances has been recorded at high-resolution for the detailed investigation of crystal field excitations.

Fosfaters reaktioner i energiomvandlingsprocesser är kritisk för den generella processen som helhet, för askrelaterade problem, emissioner liksom för en effektiv och hållbar användning av askan. Denna avhandling är en sammanställning och diskussion med utgångspunkt i åtta artiklar som behandlar strukturella och termodynamiska studier på faser i CaO-K2O-P2O5-systemet, vilka är av relevans inom förbränning av biomassa. Målsättningen med denna avhandling var: i) att sammanställa och granska tillgängliga strukturella och termodynamiska data i CaO-K2O-P2O5-systemet samt att identifiera avsaknad av data, ii) att fylla i dessa luckor med grundläggande termodynamiska, strukturella och fasstabilitets studier samt iii) att visa på användning samt fördelarna med dessa nya data vid praktisk tillämpning. En initial litteraturundersökning i CaO-K2O-P2O5-systemet visade att det saknades både strukturella och termodynamiska data. När det gällde tillgängliga termodynamiska data var situationen särskilt otillfredsställande. Det fanns endast data för några kalcium– och kaliumfosfater med varierande tillförlitlighet. Situationen beträffande pulverröntgen för fasidentifiering var bättre, fast fördunklad av det faktum att strukturellt liknande fasövergångar ofta förekommer i det undersökta systemet. Däremot fattades det tillfredställande enkristallstrukturdata för ternära faser i det undersökta systemet. Enkristallröntgendiffraktion användes för att bestämma strukturerna för CaK2P2O7, CaKP3O9, Ca10K(PO4)7 och CaKPO4. Faserna CaK2P2O7 and CaKPO4 tillsammans med Ca3(PO4)2, KPO3 och K4P2O7 studerades med pulverröntgendiffraktion och termiska analysmetoder för att klargöra fasmodifikationer och övergångstemperaturer. Gibbs bildningsenergi bestämdes för Ca(PO3)2, Ca2P2O7, Ca3(PO4)2, Ca10K(PO4)7, CaK2P2O7, CaKPO4 och CaK4(PO4)2 med ems-metodik och yttriastabiliserad zirkonia som fast elektrolyt och Ni/Ni3P som hjälpsystem. Både de strukturella och termodynamiska data användes sedan vid analyser i ett förbrännningexperiment av olika sädesslag. Framtagna data användes både vid identifiering och även vid kvantifiering av bildade faser i biomassaresterna. / The behaviour of phosphates in thermochemical biomass conversion processes are critical for the general process chemistry, for ash related problems, for emissions as well as for an efficient, sustainable and beneficial use of the ash residues. This thesis is a summary and a discussion of eight papers dealing with structural and thermodynamical studies of phases in the CaO-K2O-P2O5 system, with relevance for biomass combustion. The objectives were: i) to compile and review the available structural and thermodynamical data of phases in the CaO-K2O-P2O5 system as well as to identify existing gaps in the field of these data, ii) to fill in as many as possible of the gaps by fundamental thermodynamic, structural and phase stability studies and iii) to demonstrate the uses and the benefits of the new data in practical applications. An initial review of the CaO-K2O-P2O5 system showed that both structural information and thermodynamic data were lacking. The situation regarding the available thermodynamic data was especially unsatisfactory, data could only be found for some few calcium phosphates and a few potassium phosphates with varying reliability. Concerning powder X-ray diffraction patterns for phase identification the situation was better, though obscured by the fact that structurally close related phase transitions often occur in the studied system. However, adequate single crystal structural data of ternary phases in the system was completely missing. Crystal structures of CaK2P2O7, CaKP3O9, Ca10K(PO4)7 and CaKPO4 were determined by single-crystal X-ray diffraction. The phases CaK2P2O7 and CaKPO4 were together with Ca3(PO4)2, KPO3 and K4P2O7, investigated by powder X-ray diffraction and thermal analysis to elucidate phase modifications and transitions temperatures. Gibbs standard energy of formation was determined for Ca(PO3)2, Ca2P2O7, Ca3(PO4)2, Ca10K(PO4)7, CaK2P2O7, CaKPO4 and CaK4(PO4)2 by solid state emf measurements with yttria stabilised zirconia as solid electrolyte and Ni/Ni3P as auxiliary solid couple. Both the structural and thermodynamical data were subsequently utilised in analysis of a combustion experiment of cereal grains. The data were also used to both identify and quantify the phases formed in biomass combustion residues.

The thesis is a summary and discussion of eight papers. During the last decades, precipitation has become increasingly acidic due to the extensive use of fossil fuels. In areas of poorly buffered bedrocks, e.g. Scandinavia, northeastern United States, this phenomenon has resulted in elevated amounts of Al(III) being leached into streams and lakes. Recent findings reveal that these elevated Al-concentrations could cause fish death and decreasing forest production. In the present thesis, the importance of taking naturally occurring substances into consideration when discussing Al(III) in natural waters, is emphasized. On the basis of a chemical characterization of relevant ligand classes in a natural water, the complex formation between Al^+, hydroxide ions and the inorganic ligand carbonic acid, the low-molecular weight organic ligand citric acid and the high-molecular weight model substances gallic acid, 1,2-dihydroxynaphtha-lene-4-sulfonate, 1,2-naphthoquinone-4-sulfonate, pyrocatechol and salicylic acid were investigated. The investigations were performed as series of Potentiometrie titrations and data were processed by means of the least-squares computer program LETAGROPVRID using a technique called pqr-analysis, permitting an unbiased search for complex model (and corresponding equilibrium constants) to be made. In most systems studied, the complexation at high ligand excesses can be described by a series of mononuclear complexes AIL-AIL^. Tentatively, the whole series consists of octahedrally coordinated (water and ligand oxygens) AI(III). At lower ligand excesses, the significance and in some cases even predominance of ternary mono- and polynuclear hydroxo complexes is demonstrated. In two of the systems, binary aluminium hydroxo species are evaluated. The potential importance of the substances with respect to Al-com-plexation in natural waters are indicated in a number of model calculations. The solubility of the clay mineral kaolinite is calculated as a function of -lg[H+] and ligand concentration. It is shown that citric acid, gallic acid, 1,2-dihydroxynaphthalene-4-sulfonate, pyrocatechol and salicylic acid contribute quite significant to the total solubilities, even at very low concentrations. As a complement and background to the equilibrium studies, the corrosion rate for one of the naturally occurring Al-bearing minerals, corundum, is reported. In this investigation, performed with a leach-ant solution of ground-water composition, an experimental technique was employed which made it possible to divide the corrosion into chemical and mechanical losses. / <p>Diss. (sammanfattning) Umeå : Umeå universitet, 1983</p> / digitalisering@umu

No description available.

La fermeture de couche de l'oscillateur harmonique à N=40 dans le 68Ni est faible et perd sa rigidité après l'enlèvement (ou l'ajout) de paires de protons. Les calculs effectués dans cette région de masse prédisent un nouvel îlot d'inversion à N=40 semblable à celui à N=20 et montrant que le placement de l'orbital neutron 2d5/2 est un ingrédient essentiel pour l'interprétation de la structure nucléaire à N≈40. La différence d'énergie 1g9/2-2d5/2 a été déterminée dans le noyau 69Ni en utilisant la réaction de transfert d'un neutron d(68Ni,p) en cinématique inverse. L'expérience réalisée au GANIL utilisait un faisceau de 68Ni à 25,14 MeV/u. Les noyaux 68Ni séparés par le spectromètre LISE3 ont ensuite interagit avec une cible de CD2 d'épaisseur 2,6 mg/cm2. Le dispositif expérimental était composé principalement des détecteurs CATS/MUST2-S1/EXOGAM couplés à une chambre d'ionisation et un scintillateur plastique. Les moments angulaires et les facteurs spectroscopiques de l'état fondamental (Jπ = 9/2+) et d'un doublet d'états ( Jπ = 5/2+) autour de 2,48 MeV, associés à la population des orbitales 1g9/2 et 2d5/2, ont été obtenus après la comparaison des sections efficaces différentielles et des calculs ADWA. Les spins des états observés ont été attribués après comparaison aux calculs de modèles en couches dans un grand espace de valence. La position de l'orbitale 2d5/2 dans 69Ni a été établie pour la première fois. Nos mesures confirment l'hypothèse de la faible différence d'énergie (≈2,5 MeV) entre l'orbitale neutron 2d5/2 et l'orbitale 1g9/2 et son importance pour décrire la structure des noyaux autour de N=40. / The harmonic oscillator shell closure at N=40 in 68Ni is weak and loses its strength when removing (or adding) pair of protons. Calculations performed in this mass region predict a new island of inversion at N=40 similar to the one at N=20. Using a large valence space, the neutron orbital 2d5/2 is shown to be a crucial ingredient for the interpretation of the nuclear structure at N≈40. The neutron 1g9/2-2d5/2 energy difference has been determined in 69Ni using the d(68Ni,p) transfer reaction in inverse kinematics. The experiment performed at GANIL used a 68Ni beam at 25.14 MeV/u seperated by the LISE3 spectrometer was impinging a CD2 target of 2.6 mg/cm2 thickness. The experimental setup consisted of CATS/MUST2-S1/EXOGAM detectors coupled to an ionization chamber and a plastic scintillator. The angular momenta and spectroscopic factors of the ground state (Jπ = 9/2+) and a doublet of states ( Jπ = 5/2+) around 2.48 MeV corresponding to the population of the 1g9/2 and the 2d5/2 orbitals, were obtained from the comparison between the experimental cross-sections as a function of the proton detection angle and ADWA calculations. The spins of the observed states were assigned by comparaison to large scale Shell-Model calculations. The position of the 2d5/2 orbital in 69Ni has been established for the first time. Our measurements support the hypothesis of a low-lying 2d5/2 orbital (≈2,5 MeV) with respect to the 1g9/2 neutron orbital and thus its major role in the structure of the nuclei around N=40.