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The Crystal and Molecular Structure of 2, 2' bipyridylglycinatochloro Copper (II) DihydrateNeitzel, Conrad J. 05 1900 (has links)
The three-dimensional x-ray structure of 2,2'-bipyridylglycinatochloro copper(II) dihydrate has been fully refined to a final R factor of 0.081. The bipyridyl and glycine ligands are arranged about the central copper atom in a square planar configuration while the chlorine atom is 2.635 angstroms above this plane directly over the copper atom. This unusually long distance is explained by the positioning of a glycine group on the opposite side of the square plane, resulting in a distorted octahedral arrangement. Also, the chlorine atom is linked to three oxygen atoms via hydrogen bonding, thus stabilizing the distorted octahedral complex.
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Laser-induced fluorescence spectroscopy of the alkoxy radicalsLiu, Jinjun 26 February 2007 (has links)
No description available.
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MAGNETIC AND ORBITAL ORDERS COUPLED TO NEGATIVE THERMAL EXPANSION IN MOTT INSULATORS, CA2RU1-XMXO4 (M = 3D TRANSITION METAL ION)Qi, Tongfei 01 January 2012 (has links)
Ca2RuO4 is a structurally-driven Mott insulator with a metal-insulator (MI) transition at TMI = 357K, followed by a well-separated antiferromagnetic order at TN = 110 K. Slightly substituting Ru with a 3d transition metal ion M effectively shifts TMI and induces exotic magnetic behavior below TN. Moreover, M doping for Ru produces negative thermal expansion in Ca2Ru1-xMxO4 (M = Cr, Mn, Fe or Cu); the lattice volume expands on cooling with a total volume expansion ratio reaching as high as 1%. The onset of the negative thermal expansion closely tracks TMI and TN, sharply contrasting classic negative thermal expansion that shows no relevance to electronic properties. In addition, the observed negative thermal expansion occurs near room temperature and extends over a wide temperature interval. These findings underscores new physics driven by a complex interplay between orbital, spin and lattice degrees of freedom. These materials constitute a new class of Negative Thermal Expansion (NTE) materials with novel electronic and magnetic functions.
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Magnetic anisotropy and coercivity of tetragonally distorted spinel ferrite particles via the Jahn-Teller distortion and the magnetoelastic coupling / Anisotropie magnétique et coercivité de particules de ferrite spinelle déformées de façon tétragonale via l'effet Jahn-Teller et le couplage magnétoélastiqueAbdul Latiff, Hawa Alima Binti 13 February 2019 (has links)
Cette étude propose l'idée des aimants dits de ferrite tétragonale en rendant la symétrie cristalline des ferrites de spinelle cubique afin d'améliorer l'anisotropie magnétique (et donc, d'améliorer la coercivité). Pour concrétiser cette idée, nous avons synthétisé des particules (Cu, Co) -ferrite à distorsion tétragonale et caractérisé systématiquement les propriétés magnétiques en conséquence avec leurs distorsions de réseau. Les facteurs intrinsèques et extrinsèques contribuant à la coercivité ont été étudiés. Pour élucider l'anisotropie magnétique, nous avons démontré un modèle de couplage physique de l'effet Jahn-Teller (JT) et de l'effet magnétoélastique (ME) au sein de la théorie phénoménologique. Ensuite, nous avons effectué une analyse de coercivité dans deux modèles généraux de coercivité afin de clarifier les paramètres de la microstructure contribuant au mécanisme d'inversion de la magnétisation. À partir de l'analyse du modèle magnétoélastique, nous avons démontré l'expression linéaire de l'anisotropie magnétique en utilisant le paramètre tétragonal obtenu à partir de la distorsion JT. Les valeurs du coefficient magnétoélastique pour Cu (B1Cu = 2 MJ / m3) et Co (B1Co = 40 MJ / m3) déduites de la courbe expérimentale étaient acceptables avec la valeur calculée pour le ferrite de cuivre en vrac (B1Cu en vrac = 4 MJ / m3) et le cobalt. ferrite (masse B1Co = 55 MJ / m3). Les résultats suggèrent que l’anisotropie magnétique peut être attribuée au couplage de la distorsion JT avec l’effet magnétoélastique de Co. Au lieu d’une augmentation indéfinie avec x, l’anisotropie magnétique Ku tend à atteindre une valeur de saturation en raison de la concurrence entre les effet magnétoélastique de Co et le JT de Cu. Entre le x tétragonal x = 0,1 et le x cubique = 0,2, les valeurs de Ku constantes d'anisotropie magnétique intrinsèque ne varient pas de manière aussi significative que la différence entre les champs de coercivité et d'anisotropie. La réduction des champs d'anisotropie supérieurs à x = 0,1 peut alors être attribuée à l'augmentation de l'aimantation spontanée. L'analyse de la coercivité au sein du modèle micromagnétique a révélé une contribution importante à la coercivité de la microstructure et de l'effet démagnétisant local. Le paramètre de microstructure αMM = 0,25 obtenu était une valeur classique de l'analyse micromagnétique, suggérant le départ du champ d'anisotropie avec ce facteur de réduction. Les facteurs démagnétisants locaux effectifs NeffMM d’environ 1,4 obtenus étaient plutôt importants, ce qui suggère un effet démagnétisant significatif. Dans l'analyse du modèle global (GM), les valeurs de NeffGM obtenues étaient were 0,38 pour l'échantillon x = 0,1. La valeur négative suggère la présence d'une interaction d'échange agissant efficacement en opposition à l'interaction dipolaire. En deçà de 100 K, une différence dans le modèle suggère l’idée d’un réchauffement local consécutif à l’activation thermique due au changement d’énergie Zeeman et à une dissipation de chaleur inefficace. Cet événement peut avoir conduit à la réduction du champ coercitif à une température suffisamment basse dans l'échantillon x = 0.1 en supposant que les grains sont fortement couplés en échange. / This study proposes the idea of the so-called tetragonal ferrite magnets by rendering the crystal symmetry of the cubic spinel ferrites to enhance the magnetic anisotropy (and hence, enhance the coercivity). To realize this idea, we synthesized tetragonally distorted (Cu,Co)-ferrite particles and systematically characterized the magnetic properties accordingly with their lattice distortions. The intrinsic and extrinsic factors contributing to coercivity were investigated. To elucidate the magnetic anisotropy, we demonstrated a physical coupling model of the Jahn-Teller (JT) effect and the magnetoelastic (ME) effect within the phenomenological theory. Then, we performed coercivity analysis within two general models of coercivity to clarify the microstructure parameters contributing to the magnetization reversal mechanism. From the magnetoelastic model analysis, we demonstrated the linear expression of the magnetic anisotropy using the tetragonal parameter obtained from the JT distortion. The magnetoelastic coefficient values for Cu (B1Cu = 2 MJ/m3) and Co (B1Co = 40 MJ/m3) deduced from the experimental curve were agreeable with the value calculated for bulk copper ferrite (B1Cu bulk= 4 MJ/m3) and cobalt ferrite (B1Co bulk= 55 MJ/m3). The results suggests that the source of magnetic anisotropy can be attributed to the coupling of the JT distortion with the magnetoelastic effect of Co. Instead of an indefinite increase with x, the magnetic anisotropy Ku tends to reach a saturation value due to the competition between the magnetoelastic effect of Co and the JT effect of Cu. Between the tetragonal x = 0.1 and the cubic x = 0.2 samples, the intrinsic magnetic anisotropy constant Ku values do not vary as significantly compared to the difference in the coercivity and the anisotropy fields. The reduction of anisotropy fields above x = 0.1 then can be attributed to the increase in the spontaneous magnetization.The coercivity analysis within the micromagnetic model revealed significant contribution to the coercivity by the microstructure and the local demagnetizing effect. The microstructure parameter αMM = 0.25 obtained was a classical value in the micromagnetic analysis, suggesting the departure of anisotropy field with this reduction factor. The effective local demagnetizing factor NeffMM of about 1.4 obtained were rather large suggesting a significant demagnetizing effect. Within the global model (GM) analysis, the values of NeffGM obtained were -0.38 for the x = 0.1 sample. The negative value suggests the presence of an exchange interaction acting effectively in opposition to the dipolar interaction. Below 100 K, discrepancy in the GM suggests the idea of a local heating event following the thermal activation due to the change in Zeeman energy and ineffective heat dissipation. This event may have led to the reduction of coercive field at sufficiently low temperature in the x = 0.1 sample assuming the grains are strongly exchange-coupled.
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Synthesis of lithium manganese phosphate by controlled sol-gel method and design of all solid state lithium ion batteriesPenumaka, Rani Vijaya January 2015 (has links)
Indiana University-Purdue University Indianapolis (IUPUI) / Due to the drastic increase in the cost of fossil fuels and other environmental issues, the demand for energy and its storage has risen globally. Rather than being dependent on intermittent energy sources like wind and solar energy, focus has been on alternative energy sources. To eliminate the need for fossil fuels, advances are being made to provide energy for hybrid electric vehicles (HEV), plug-in hybrid vehicles (PHEV) and pure electric vehicles (EV) thus providing scope for much greener environment. Hence, focus has been on development in lithium ion batteries to provide with materials that have high energy density and voltage.
Ortho olivine lithium transitional metals are known to be abundant and inexpensive; these compounds are less noxious than other cathode materials. Advancement in research is being done in finding iron and manganese compounds as cathode materials for advanced technologies. However, Lithium manganese phosphates are known to suffer with poor electrochemical performances due the manganese dissolution in the organic liquid electrolyte due to Jahn-Teller Lattice distortion. This problem was tried to endorse in this thesis. In the second chapter by synthesizing nano sized cathode particles with good electronic conductivity, good performance was achieved.
In the third chapter additive olivine cathode was synthesized my modified sol gel process. A wt. % of TMSP was added as an additive in the organic liquid electrolyte. By comparing the properties between the two kinds of electrolytes it was observed that by the addition of the additive in the organic electrolyte good electrochemical properties could be achieved hindering the Mn dissolution in the electrolyte.
In the final chapter, a composite solid electrolyte was fabricated by using NASICON-type glass ceramic of Lithium aluminum titanium phosphate (LATP) with organic binder of Polyethylene oxide. The flexible solid electrolyte exhibited good ionic conductivity. An all solid state cell was fabricated using the composite solid electrolyte using LiMn2O4 as the symmetric electrodes. At different pressures, the performance of the solid state cell was studied.
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Laser Spectroscopy Studying Organic and Inorganic Intermediates in The Atmospheric Oxidation ProcessChen, Ming-Wei 20 October 2011 (has links)
No description available.
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Σύνθεση, δομικός χαρακτηρισμός, φασματοσκοπικές και μαγνητικές μελέτες πολυπυρηνικών ομομεταλλικών 3d και ετερομεταλλικών 3d-4f συμπλόκων / Synthesis, structural characterization, spectroscopic and magnetic studies of polynuclear 3d homometallic and 3d-4f heterometallic complexesΓεωργοπούλου, Αναστασία 15 February 2012 (has links)
Με σκοπό τη μελέτη της χημείας ένταξης του υποκαταστάτη δι-2,6-(2-πυριδυλοκαρβονυλο) πυριδίνη (dpcp) με μέταλλα μετάπτωσης 3d, παρασκευάστηκαν οι τετραπυρηνικές πλειάδες [Cu4(N3)2{pyCO(OMe)pyCO(OMe)py}2(MeOH)2](ClO4)∙2MeOH (1∙2MeOH) και [Co4(N3)2(NO3)2{pyCO(OMe)pyCO(OMe)py}2]∙0.5MeOH (2∙0.5MeOH), η εξαπυρηνική πλειάδα [Ni6(CO3)(N3)6{pyCOpyC(O)(OMe)py}3(MeOH)2(H2O)][Ni6(CO3)(N3)6 {pyCOpyC(O)(OMe)py}3(MeOH)3](ClO4)2 (3∙1.8MeOH) και η διπυρηνική πλειάδα [Fe2{pyCO(OMe)py(Η)CO(OMe)py}2(MeO)2](ClO4)2∙(4∙MeOH). Στην συνέχεια μελετήθηκε η χημεία ένταξης του ίδιου υποκαταστάτη με μέταλλα 3d και 4f και παρασκευάστηκαν τα ετερομεταλλικά διπυρηνικά σύμπλοκα [ΜIILnIII{pyCOH(OEt)pyCOH(OEt)py}3](ClO4)2∙EtOH (5-16∙EtOH) με ΜΙΙ = CuΙΙ, CoΙΙ, NiΙΙ, ZnΙΙ, MnΙΙ, FeΙΙ [LnΙΙΙ = GdΙΙΙ (5 - 10), TbΙΙΙ (11 – 16) αντίστοιχα]. Όλα τα σύμπλοκα χαρακτηρίστηκαν κρυσταλλογραφικά, τα σύμπλοκα 4, 10 και 16 χαρακτηρίστηκαν με φασματοσκοπία Mössbauer ενώ τα σύμπλοκα 1 – 10 χαρακτηρίστηκαν μαγνητικά. Πιο συγκεκριμένα, οι μαγνητικές μελέτες των συμπλόκων 1 – 3, 5 και 10 έδειξαν σιδηρομαγνητικές αλληλεπιδράσεις ενώ εκείνες των συμπλόκων 4, 6, 7 και 9 έδειξαν αντισιδηρομαγνητικές αλληλεπιδράσεις.
Προκειμένου να μελετηθεί σε βάθος η οικογένεια των βασικών καρβοξυλικών αλάτων του σιδήρου [Fe3O(O2CR)6(H2O)3]A, παρασκευάστηκαν δύο σειρές αυτών των συμπλόκων με R = CCl3, CHBr2, CH2F, CH2Cl, C(OH)Ph2, H, Ph, (CH2)3Cl, Me, CHMe2, Et και CMe3. Στην πρώτη σειρά συμπλόκων (17 - 28) το αντισταθμιστικό ιόν (Α) είναι ClO4-, ενώ στη δεύτερη (29 - 40) είναι NO3-. Η προσπάθεια απομόνωσης του ανάλογου με R = CF3 ήταν άκαρπη και για τα δύο αντισταθμιστικά ιόντα και οδήγησε σε ένα τετραπυρηνικό σύμπλοκο [Fe4O2(O2CCF3)8(H2O)6] (41) με δομή τύπου «πεταλούδας». Πραγματοποιήθηκαν μετρήσεις Mössbauer σε στερεά δείγματα και για τις δύο σειρές και οι ισομερείς μετατοπίσεις και οι τετραπολικές αλληλεπιδράσεις διαφέρουν μεταξύ 0.51 – 0.54 mms-1 και 0.36 – 0.76 mms-1 αντίστοιχα. Μετρήσεις Mössbauer και σε διαλύματα αυτών έδειξαν τη σταθερότητά τους και σε διάλυμα, με εξαίρεση το σύμπλοκο 29 (R = Cl3C, Α = NO3-) που οδήγησε σε σύμπλοκο τύπου «πεταλούδας».
Το υψηλής συμμετρίας σύμπλοκο [Fe3O(O2CPh)6(py)3](ClO4)∙py (42) έχει μελετηθεί στο παρελθόν κρυσταλλογραφικά αλλά και με μετρήσεις ανελαστικής σκέδασης νετρονίων IINS και είχε προταθεί ύπαρξη του μαγνητικού φαινομένου Jahn-Teller σε πολύ χαμηλές θερμοκρασίες. Θέλοντας να εξακριβωθεί εάν η μαγνητική συμμετρία σχετίζεται με την πραγματική, πραγματοποιήθηκαν κρυσταλλογραφικές μετρήσεις μεταβλητής θερμοκρασίας στο εργαστήριο ΒΜ01Α του ESRF. Τα αποτελέσματα των πειραματικών μετρήσεων έδειξαν ότι η πραγματική συμμετρία παραμένει ίδια. Στη συνέχεια από μετρήσεις μαγνητικής επιδεκτικότητας ac, παρατηρήθηκε η ύπαρξη μαγνητικών φαινομένων χαλάρωσης υπό την επίδραση ασθενών μαγνητικών πεδίων. / Seeking to study the coordination chemistry of the ligand di-2, 6-(2-pyridylcarbonyl) pyridine (dpcp) with 3d transition metal ions, the tetranuclear complexes [Cu4(N3)2{pyCO(OMe)pyCO(OMe)py}2(MeOH)2](ClO4)∙2MeOH (1∙2MeOH) and [Co4(N3)2(NO3)2{pyCO(OMe)pyCO(OMe)py}2]∙0.5MeOH (2∙0.5MeOH), the hexanuclear complex [Ni6(CO3)(N3)6{pyCOpyC(O)(OMe)py}3(MeOH)2(H2O)][Ni6(CO3)(N3)6{pyCOpyC(O) (OMe)py}3(MeOH)3](ClO4)2 (3∙1.8MeOH) and the dinuclear complex [Fe2{pyCO(OMe)py(Η)CO(OMe)py}2(MeO)2](ClO4)2∙(4∙MeOH) were synthesized. In addition, in order to study the coordination chemistry of the same ligand with mixed 3d transition metal ions and 4f lanthanide ions, the heterometallic dinuclear complexes [ΜIILnIII{pyCOH(OEt)pyCOH(OEt)py}3] (ClO4)2∙EtOH (5-16∙EtOH) were synthesized, with ΜΙΙ = CuΙΙ, CoΙΙ, NiΙΙ, ZnΙΙ, MnΙΙ, FeΙΙ [LnΙΙΙ = GdΙΙΙ (5 - 10), TbΙΙΙ (11 – 16) respectively]. All complexes were structurally characterized and complexes 4, 10 and 16 were characterized by Mössbauer spectroscopy. Magnetic properties measurements of complexes 1-3, 5 and 10 indicated the existence of ferromagnetic interactions, while those of 4, 6, 7 and 9 indicated the existence of antiferromagnetic interactions.
For the in depth study of the family of basic iron (III) carboxylates [Fe3O(O2CR)6(H2O)3]A, two series of complexes were prepared with R = Cl3C, CHBr2, CH2F, CH2Cl, C(OH)Ph2, H, Ph, Cl(CH2)3, Me, CHMe2, Et and Me3C. For the former series (17 - 28) the counteranion (A-) is ClO4- and for the latter (29 - 40) is NO3-. Attempts to prepare the respective trifluoroacetate (R = CF3) complexes were unsuccessful and the reaction system lead to the tetranuclear “butterfly” complex [Fe4O2(O2CCF3)8(H2O)6] (41), irrespective of whether perchlorates or nitrates were used as counteranions. Mössbauer studies revealed very similar isomer shifts for all complexes in the region of 0.51 – 0.54 mms-1, and variable quadrupole splittings, ranging from 0.36 to 0.76 mms-1. Mössbauer studies of the complexes were carried out in frozen MeCN solutions in order to assess their stability in solution and they proved to be stable in MeCN solutions, except complex 29 (R = Cl3C, Α = NO3-), which dissociated to a butterfly-type complex.
The high-symmetry cluster [Fe3O(O2CPh)6(py)3](ClO4)∙py (42) has been structurally characterized and its Inelastic Incoherent Neutron Scattering studies have been reported. These studies suggested the existence of a magnetic Jahn-Teller effect at lower temperatures. Seeking to study if there is any correlation between magnetic and structural symmetry, we undertook variable-temperature crystallographic studies on ESRF BM01A beamline. With the results of these data we concluded that the symmetry of the crystal remained. Moreover, we have discovered that this complex exhibits magnetic relaxation phenomena under weak magnetic fields, observed by ac magnetic susceptometry.
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