Electronic and magnetic structure of LaMnO3 from hybrid periodic density-functional theory

The electronic and magnetic structures of the LaMnO3 compound have been studied by means of periodic calculations within the framework of spin polarized hybrid density-functional theory. In order to quantify the role of approximations to electronic exchange and correlation three different hybrid functionals have been used which mix nonlocal Fock and local Dirac-Slater exchange. Periodic Hartree-Fock results are also reported for comparative purposes. The A-antiferromagnetic ground state is properly predicted by all methods including Hartree-Fock exchange. In general, the different hybrid methods provide a rather accurate description of the band gap and of the two magnetic coupling constants, strongly suggesting that the corresponding description of the electronic structure is also accurate. An important conclusion emerging from this study is that the nature of the occupied states near the Fermi level is intermediate between the Hartree-Fock and local density approximation descriptions with a comparable participation of both Mn and O states.

A first-principles analysis of the magnetism of CuII polynuclear coordination complexes: the case of [Cu4(bpy)4(aspartate)2(H2O)3](ClO4)4·2.5H2O

The magnetic structure of the [Cu4(bpy)4(aspartate)2(H2O)3](ClO4)4·2.5 H2Ocrystal - using fractional coordinates determined at room-temperature ¿ has beenanalysed in detail. This analysis has been carried out by extending our first principlesbottom-up theoretical approach, which was initially designed to study through-spacemagnetic interactions, to handle through-bond magnetic interactions. The only input datarequired by this approach are the values of the computed JAB exchange parameters for allthe unique pairs of spin-containing centres. The results allow the magnetic structure ofthe crystal, which presents two types of isolated tetranuclear CuII clusters, to be definedin quantitative terms. Each of these clusters presents ferro and antiferromagneticinteractions, the former being stronger, although outnumbered by the latter. Thecomputed magnetic susceptibility curve shows the same qualitative features as theexperimental data. However, there are small differences that are presumed to beassociated with the use of room-temperature crystal coordinates.

Analysis of the structural and electronic properties of 1-(5-Hydroxymethyl - 4 -[ 5 - (5-oxo-5-piperidin-1-yl-penta-1,3dienyl)-benzo[1,3]dioxol-2-yl] -tetrahydro-furan-2-yl)-5-methyl-1H-pyrimidine-2,4dione molecule

The structural and electronic properties of 1-(5-Hydroxymethyl - 4 -[ 5 - (5-oxo-5-piperidin- 1 -yl-penta- 1,3 -dienyl)-benzo [1,3] dioxol- 2 -yl]-tetrahydro -furan-2 -yl)-5-methy l-1Hpyrimidine-2,4dione (AHE) molecule have been investigated theoretically by performing density functional theory (DFT), and semi empirical molecular orbital calculations. The geometry of the molecule is optimized at the level of Austin Model 1 (AM1), and the electronic properties and relative energies of the molecules have been calculated by density functional theory in the ground state. The resultant dipole moment of the AHE molecule is about 2.6 and 2.3 Debyes by AM1 and DFT methods respectively, This property of AHE makes it an active molecule with its environment, that is AHE molecule may interacts with its environment strongly in solution.

Regulation of photosynthetic electron transfer in plant chloroplasts

This thesis focuses on the molecular mechanisms regulating the photosynthetic electron transfer reactions upon changes in light intensity. To investigate these mechanisms, I used mutants of the model plant Arabidopsis thaliana impaired in various aspects of regulation of the photosynthetic light reactions. These included mutants of photosystem II (PSII) and light harvesting complex II (LHCII) phosphorylation (stn7 and stn8), mutants of energy-dependent non-photochemical quenching (NPQ) (npq1 and npq4) and of regulation of photosynthetic electron transfer (pgr5). All of these processes have been extensively investigated during the past decades, mainly on plants growing under steady-state conditions, and therefore many aspects of acclimation processes may have been neglected. In this study, plants were grown under fluctuating light, i.e. the alternation of low and high intensities of light, in order to maximally challenge the photosynthetic regulatory mechanisms. In pgr5 and stn7 mutants, the growth in fluctuating light condition mainly damaged PSI while PSII was rather unaffected. It is shown that the PGR5 protein regulates the linear electron transfer: it is essential for the induction of transthylakoid ΔpH that, in turn, activates energy-dependent NPQ and downregulates the activity of cytochrome b6f. This regulation was shown to be essential for the photoprotection of PSI under fluctuations in light intensity. The stn7 mutants were able to acclimate under constant growth light conditions by modulating the PSII/PSI ratio, while under fluctuating growth light they failed in implementing this acclimation strategy. LHCII phosphorylation ensures the balance of the excitation energy distribution between PSII and PSI by increasing the probability for excitons to be trapped by PSI. LHCII can be phosphorylated over all of the thylakoid membrane (grana cores as well as stroma lamellae) and when phosphorylated it constitutes a common antenna for PSII and PSI. Moreover, LHCII was shown to work as a functional bridge that allows the energy transfer between PSII units in grana cores and between PSII and PSI centers in grana margins. Consequently, PSI can function as a quencher of excitation energy. Eventually, the LHCII phosphorylation, NPQ and the photosynthetic control of linear electron transfer via cytochrome b6f work in concert to maintain the redox poise of the electron transfer chain. This is a prerequisite for successful plant growth upon changing natural light conditions, both in short- and long-term.

A spectral analysis of the myoelectric activity of the left colon in patients with schistosomiasis mansoni

The objective of the present study was to perform a spectral analysis of the electrical activity of the left colon of patients with hepatosplenic schistosomiasis. Thirty patients were studied, divided into 2 groups: group A was composed of 14 patients (9 males and 5 females) with hepatosplenic schistosomiasis and group B was composed of 16 female patients without schistosomiasis mansoni. Three pairs of electrodes were implanted in the left colon at the moment of the surgical treatment. The signals of the electric activity of the colon were captured after postoperative recovery from the ileus and fed into a computer by means of a DATAQ data collection system which identified and captured frequencies between 0.02 and 10 Hz. Data were recorded, stored and analyzed using the WINDAQ 200 software. For electrical analysis, the average voltage of the electrical wave in the three electrodes of all patients, expressed as millivolts (mV), was considered, together with the maximum and minimum values, the root mean square (RMS), the skewness, and the results of the fast Fourier transforms. The average RMS of the schistosomiasis mansoni patients was 284.007 mV. During a long period of contraction, the RMS increased in a statistically significant manner from 127.455 mV during a resting period to 748.959 mV in patients with schistosomiasis mansoni. We conclude that there were no statistically significant differences in RMS values between patients with schistosomiasis mansoni and patients without the disease during the rest period or during a long period of contraction.

Toward including the effect of manufacturing processes in the pre-estimated losses of the switched reluctance motor

The estimation of losses plays a key role in the process of building any electrical machine. How to estimate those losses while designing any machine; by obtaining the characteristic of the electrical steel from the catalogue and calculate the losses. However, this way is inaccurate since the electrical steel performs several manufacturing processes during the process of building any machine, which affects directly the magnetic property of the electrical steel and accordingly the characteristic of the electrical steel will be affected. That means the B–H curve of the steel that was obtained from the catalogue will be changed. Moreover, during loading and rotating the machine, some important changes occur to the B–H characteristic of the electrical steel such as the stress on the laminated iron. Accordingly, the pre-estimated losses are completely far from the actual losses because they were estimated based on the data of the electrical steel obtained from the catalogue. So in order to estimate the losses precisely significant factors of the manufacturing processes must be included. The paper introduces the systematic estimation of the losses including the effect of one of the manufacturing factors. Similarly, any other manufacturing factor can be included in the pre-designed losses estimations.

Magnetic field induced entropy change and magnetoelasticity in Ni-Mn-Ga alloys

The magnetocaloric effect that originates from the martensitic transition in the ferromagnetic Ni-Mn-Ga shape-memory alloy is studied. We show that this effect is controlled by the magnetostructural coupling at both the martensitic variant and magnetic domain length scales. A large entropy change induced by moderate magnetic fields is obtained for alloys in which the magnetic moment of the two structural phases is not very different. We also show that this entropy change is not associated with the entropy difference between the martensitic and the parent phase arising from the change in the crystallographic structure which has been found to be independent of the magnetic field within this range of fields.

Electronic and magnetic structure of LaMnO3 from hybrid periodic density-functional theory

The electronic and magnetic structures of the LaMnO3 compound have been studied by means of periodic calculations within the framework of spin polarized hybrid density-functional theory. In order to quantify the role of approximations to electronic exchange and correlation three different hybrid functionals have been used which mix nonlocal Fock and local Dirac-Slater exchange. Periodic Hartree-Fock results are also reported for comparative purposes. The A-antiferromagnetic ground state is properly predicted by all methods including Hartree-Fock exchange. In general, the different hybrid methods provide a rather accurate description of the band gap and of the two magnetic coupling constants, strongly suggesting that the corresponding description of the electronic structure is also accurate. An important conclusion emerging from this study is that the nature of the occupied states near the Fermi level is intermediate between the Hartree-Fock and local density approximation descriptions with a comparable participation of both Mn and O states.

Spin polarized neutron matter and magnetic susceptibility within the Brueckner-Hartree-Fock approximation

The Brueckner-Hartree-Fock formalism is applied to study spin polarized neutron matter properties. Results of the total energy per particle as a function of the spin polarization and density are presented for two modern realistic nucleon-nucleon interactions, Nijmegen II and Reid93. We find that the dependence of the energy on the spin polarization is practically parabolic in the full range of polarizations. The magnetic susceptibility of the system is computed. Our results show no indication of a ferromagnetic transition which becomes even more difficult as the density increases.

The mapping of the local contributions of Fermi and Coulomb correlation into intracule and extracule density distributions

The contributions of the correlated and uncorrelated components of the electron-pair density to atomic and molecular intracule I(r) and extracule E(R) densities and its Laplacian functions ∇2I(r) and ∇2E(R) are analyzed at the Hartree-Fock (HF) and configuration interaction (CI) levels of theory. The topologies of the uncorrelated components of these functions can be rationalized in terms of the corresponding one-electron densities. In contrast, by analyzing the correlated components of I(r) and E(R), namely, IC(r) and EC(R), the effect of electron Fermi and Coulomb correlation can be assessed at the HF and CI levels of theory. Moreover, the contribution of Coulomb correlation can be isolated by means of difference maps between IC(r) and EC(R) distributions calculated at the two levels of theory. As application examples, the He, Ne, and Ar atomic series, the C2-2, N2, O2+2 molecular series, and the C2H4 molecule have been investigated. For these atoms and molecules, it is found that Fermi correlation accounts for the main characteristics of IC(r) and EC(R), with Coulomb correlation increasing slightly the locality of these functions at the CI level of theory. Furthermore, IC(r), EC(R), and the associated Laplacian functions, reveal the short-ranged nature and high isotropy of Fermi and Coulomb correlation in atoms and molecules

The heliospheric magnetic field over the Hale cycle

The concept that open magnetic flux of the Sun (rooted with one and only one footpoint at the Sun) is a conserved quantity is taking root in the heliospheric community. Observations show that the Sun's open magnetic flux returns to the baseline from one solar minimum to the next. The temporary enhancement in the 1 AU heliospheric magnetic flux near solar maximum can be accounted for by the temporary creation of closed magnetic flux (with two footpoints at the Sun) during the ejection of coronal mass ejections (CMEs), which are more frequent near solar maximum. As a part of the International Heliophysical Year activities, this paper reviews two recently discussed consequences of open flux conservation: the reversal of open magnetic flux over the solar cycle driven by Coronal Mass Ejections and the impacts of open flux conservation on the global structure of the heliospheric magnetic field. These studies demonstrate the inherent linkages between coronal mass ejections, footpoint motions back at the Sun, and the global structure and evolution of the heliospheric magnetic field.

Another Proof of the Preceding Theory

Another Proof of the Preceding Theory was produced as part of a residency run by Artists in Archeology in conjunction with the Stonehenge Riverside project. The film explores the relationship between science, work and ritual, imagining archaeology as a future cult. As two robed disciples stray off from the dig, they are drawn to the drone of the stones and proceed to play the henge like a gigantic Theremin. Just as a Theremin is played with the hand interfering in an electric circuit and producing sound without contact, so the stones respond to the choreographed bodily proximity. Finally, one of the two continues alone to the avenue at Avebury, where the magnetic pull of the stones reaches its climax. Shot on VHS, the film features a score by Zuzushi Monkey, with percussion and theremin sounds mirroring the action. The performers are mostly artists and archeologists from the art and archaeology teams. The archeologists were encouraged to perform their normal work in the robes, in an attempt to explore the meeting points of science and ritual and interrogate our relationship to an ultimately unknowable prehistoric past where activities we do not understand are relegated to the realm of religion. Stonehenge has unique acoustic properties, it’s large sarsen stones are finely worked on the inside, left rough on the outside, intensifying sound waves within the inner horseshoe, but since their real use, having been built over centuries, remains ambiguous, the film proposes that our attempts to decode them may themselves become encoded in their cumulative meaning for future researchers.

Direct probing of photoinduced electron transfer in a self- assembled biomimetic [2Fe2S]-hydrogenase complex using ultrafast vibrational spectroscopy

A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

The foundations of the rule of law

Formal conceptions of the rule of law are popular among contemporary legal philosophers. Nonetheless, the coherence of accounts of the rule of law committed to these conceptions is sometimes fractured by elements harkening back to substantive conceptions of the rule of law. I suggest that this may be because at its origins the ideal of the rule of law was substantive through and through. I also argue that those origins are older than is generally supposed. Most authors tend to trace the ideas of the rule of law and natural law back to classical Greece, but I show that they are already recognisable and intertwined as far back as Homer. Because the founding moment of the tradition of western intellectual reflection on the rule of law placed concerns about substantive justice at the centre of the rule of law ideal, it may be hard for this ideal to entirely shrug off its substantive content. It may be undesirable, too, given the rhetorical power of appeals to the rule of law. The rule of law means something quite radical in Homer; this meaning may provide a source of normative inspiration for contemporary reflections about the rule of law.

Relaxation of the electrical resistivity in Cr-doped Nd(0.5)Ca(0.5)MnO(3) single crystals

We have performed a systematic study of the time and temperature dependencies of the electrical resistivity (rho(T, t)) inNd(0.5)Ca(0.5)Mn(1-x)Cr(x)O(3) single crystals with x = 0.02 and 0.07 in order to examine the dynamics of the phase separation. The relaxation effects can be described by the combination of a rapid exponential increase/decrease with a slower logarithmic contribution at longer times. The experimental results suggest the existence of a large temperature window in which huge relaxation effects occur, and the relative fraction of the coexisting phases rapidly changes as a function of time, depending on the initial magnetic state of the sample. The rho(T, t) relaxation measurements were shown to be a suitable tool for probing the dynamical nature of the phase separation, in which magnetically distinct phases compete against each other in a wide temperature range. In addition, the features observed in the rho(T, t) curves were found to be in excellent agreement with both the magnetic properties and the structural transitions observed in these manganites.