Control of photomagnetic behavior in heterobimetallic Prussian Blue analogs

A new challenge in the field of molecular magnetism is the design of optically and thermally switchable solid state magnetic materials for which various kinds of application may be feasible. Our research activities involve preparative methods, the study of the physical properties and associated mechanisms, as well as the exploration of further possibilities. Particular focus is on heterobimetallic Prussian Blue analogs, such as on RbMn[Fe(CN)6], in which the interplay between the two different adjacent metal ions is crucial for the observation of photo-induced phenomena. Our studies revealed that modification of the preparative conditions lead to differences in structural features that allowed tuning of the magnetic and electron transfer properties of RbxMn[Fe(CN)6]y.zH2O.

Valence-tautomeric RbMnFe Prussian blue analogues:composition and time stability investigation

Three different stoichiometric forms of RbMn[Fe(CN) ]y·zHO [x = 0.96, y = 0.98, z = 0.75 (1); x = 0.94, y = 0.88, z = 2.17 (2); x = 0.61, y = 0.86, z = 2.71 (3)] Prussian blue analogues were synthesized and investigated by magnetic, calorimetric, Raman spectroscopic, X-ray diffraction, and Fe Mössbauer spectroscopic methods. Compounds 1 and 2 show a hysteresis loop between the high-temperature (HT) Fe(S = 1/2)-CN-Mn(S = 5/2) and the low-temperature (LT) Fe(S = 0)-CN-Mn(S = 2) forms of 61 and 135 K width centered at 273 and 215 K, respectively, whereas the third compound remains in the HT phase down to 5 K. The splitting of the quadrupolar doublets in the Fe Mössbauer spectra reveal the electron-transfer-active centers. Refinement of the X-ray powder diffraction profiles shows that electron-transfer-active materials have the majority of the Rb ions on only one of the two possible interstitial sites, whereas nonelectron-transfer-active materials have the Rb ions equally distributed. Moreover, the stability of the compounds with time and following heat treatment is also discussed. © Wiley-VCH Verlag GmbH & Co. KGaA, 2009.

Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

Origin of the ESR spectrum in the Prussian Blue analogue RbMn[Fe(CN)6]*H2O

We present an ESR study at excitation frequencies of 9.4 GHz and 222.4 GHz of powders and single crystals of a Prussian Blue analogue (PBA), RbMn[Fe(CN)6]*H2O in which Fe and Mn undergoes a charge transfer transition between 175 and 300 K. The ESR of PBA powders, also reported by Pregelj et al. (JMMM, 316, E680 (2007)) is assigned to cubic magnetic clusters of Mn2+ ions surrounding Fe(CN)6 vacancies. The clusters are well isolated from the bulk and are superparamagnetic below 50 K. In single crystals various defects with lower symmetry are also observed. Spin-lattice relaxation broadens the bulk ESR beyond observability. This strong spin relaxation is unexpected above the charge transfer transition and is attributed to a mixing of the Mn3+ - Fe2+ state into the prevalent Mn2+ - Fe3+ state.

Individual differences in work behaviour of blue-collar workers : a study of rubber tappers in Malaysia

This thesis examines individual differences in work behaviour of rubber tappers. The study examined sex, age, experience and race differences and their interactions with terrain on job performance, absenteeism, and job satisfaction of 1053 rubber tappers. Rubber tappers are unskilled blue-collar workers who essentially do the same type of work and are paid the same rates of pay. There are very few studies that have compared male and female blue-collar workers doing similar jobs in organisational settings. This study is one of the few investigations that examine sex differences in job performance of blue-collar workers doing same job using production data. Studies on age differences in work behaviour encounter numerous methodological difficulties such as high turnover, internal transfers and problems associated with age differences in educational levels. The participation of rubber tappers in this study is envisaged to overcome these difficulties because attrition rates of rubber tappers are low, and internal transfers are non existent. Further, the educational levels of rubber tappers are relatively similar across different age cohorts, as most rubber tappers have little or no education. Two measures of both job performance and absenteeism were derived from payroll records. The two job performance measures were total crop production and attendance. The two absenteeism measures were avoidable and unavoidable absence rates. Overall job satisfaction was determined using a 4-item scale. Significant sex, age, experience and race differences were obtained for job performance, absenteeism and job satisfaction. Significant interactive effects were also obtained for sex, age , experience, race and terrain for job performance and absenteeism. The results are discussed in relation to the abilities and motivation of rubber tappers. The implication of these findings for employee selection and human resource management in rubber estates is discussed.

Looking for redemption in a globalised North:representations of the Arctic in Judith Hermann’s Short Stories Kaltblau (Cold –Blue) and Die Liebe zu Ari Oskarsson (Love for Ari Oskarsson)

This paper explores the literary representation of Iceland and Norway in two short stories by contemporary German writer Judith Hermann. It analyses both the depiction of these countries as part of the globalised western world and the redemptive power they are tentatively ascribed by the author. Continuing a long German tradition of looking at Scandinavia from an almost colonial perspective, Hermann on the one hand presents these northern countries as a mere extension of central Europe, largely devoid of distinguishing national characteristics. At the same time she makes reference to the topos of the north as a vast and empty space and highlights both the specific arctic nature of the environment and the effect it has on her urban characters, who find themselves on a search for meaning and orientation in a postmodern fragmented world. Despite Hermann's overall sceptical attitude towards her characters' quest for happiness, these northern locations ultimately appear as potential places of self-realisation and enlightenment.

Majority and minority influence using the afterimage paradigm:a replication with an unambiguous blue slide

This study re-examines the afterimage paradigm which claims to show that a minority produces a conversion in a task involving afterimage judgements (more private influence than public influence) as opposed to mere compliance produced by a majority. Subsequent failures to replicate this finding have suggested that the changes in the afterimages could be attributed to increased attention due to an ambiguous stimulus coupled with subject suspiciousness. This study attempted to replicate the original experiment but with an unambiguous stimulus in order to remove potential biases. The results showed shifts in afterimages consistent with the increased attention hypothesis for a minority and majority and these were unaffected by the level of suspiciousness reported by the subjects. Additional data shows that no shifts were found in a no-influence control condition showing that shifts were related to exposure to a deviant source and not to response repetition.

Bulk and surface switching in Mn-Fe-based Prussian blue analogues

Many Prussian Blue Analogues are known to show a thermally induced phase transition close to room temperature and a reversible, photo-induced phase transition at low temperatures. This work reports on magnetic measurements, X-ray photoemission and Raman spectroscopy on a particular class of these molecular heterobimetallic systems, specifically on Rb0.81Mn[Fe(CN)6]0.95_1.24H2O, Rb0.97Mn[Fe(CN)6]0.98_1.03H2O and Rb0.70Cu0.22Mn0.78[Fe(CN)6]0.86_2.05H2O, to investigate these transition phenomena both in the bulk of the material and at the sample surface. Results indicate a high degree of charge transfer in the bulk, while a substantially reduced conversion is found at the sample surface, even in case of a near perfect (Rb:Mn:Fe=1:1:1) stoichiometry. Thus, the intrinsic incompleteness of the charge transfer transition in these materials is found to be primarily due to surface reconstruction. Substitution of a large fraction of charge transfer active Mn ions by charge transfer inactive Cu ions leads to a proportional conversion reduction with respect to the maximum conversion that is still stoichiometrically possible and shows the charge transfer capability of metal centers to be quite robust upon inclusion of a neighboring impurity. Additionally, a 532 nm photo-induced metastable state, reminiscent of the high temperature Fe(III)Mn(II) ground state, is found at temperatures 50-100 K. The efficiency of photo-excitation to the metastable state is found to be maximized around 90 K. The photo-induced state is observed to relax to the low temperature Fe(II)Mn(III) ground state at a temperature of approximately 123 K.

On the effect of blue staining fungi on the permeability of sitka spruce

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Blue-to-red tunable SHG from a diode-pumped PPKTP waveguide

Summary form only given. Broadly tunable compact visible laser sources in the spectral region of 500-650 nm are valuable in biophotonics, photomedicine and for many applications including spectroscopy, laser projection and confocal microscopy. Unfortunately, commercially available lasers of this spectral range are in practice bulky and inconvenient in use. An attractive method for the realization of portable visible laser sources is the frequency-doubling of the infrared laser diodes in a nonlinear crystal containing a waveguide [1]. Nonlinear crystal waveguides that offer an order-of-magnitude increase in the IR-to-visible conversion efficiency also enable a very different approach to second-harmonic generation (SHG) tunability in periodically-poled crystals, promising order-of-magnitude increase of wavelength range for SHG conversion. This is possible by utilization of a significant difference in the effective refractive indices of the high-order and low-order modes in multimode waveguides [2]. The recent availability of low-cost, good quality semiconductor diode lasers, offering the coverage of a broad spectral range between 1 µ?? and 1.3 µp? [3,4], in combination with well-established techniques to fabricate good quality waveguides in nonlinear crystals, allows compact tunable CW laser sources in the visible spectral region to be realized [2].

Debazzled:a blue and black ship, dressed to deceive

The blue and black dress that “melted the Internet” is thought to have done so because its perceived color depended on people using different prior assumptions about discounting the illuminant. However, this is not the first monochromatic object to have confused the public. For a brief period during WWI, RMS Mauretania was dressed in (dazzle) camouflage shades of blue and black/grey, yet she is sometimes depicted by artists, modelers, and historians in a much showier dress of red, blue, yellow, green, and black. I raise the possibility that this originates from a case of public deception deriving from the momentary misperception of a playful artist who neglected to discount the illuminant, propagating the most (perhaps only) successful application of dazzle camouflage known.

Blue-detuned optical ring trap for Bose-Einstein condensates based on conical refraction

We present a novel approach for the optical manipulation of neutral atoms in annular light structures produced by the phenomenon of conical refraction occurring in biaxial optical crystals. For a beam focused to a plane behind the crystal, the focal plane exhibits two concentric bright rings enclosing a ring of null intensity called the Poggendorff ring. We demonstrate both theoretically and experimentally that the Poggendorff dark ring of conical refraction is confined in three dimensions by regions of higher intensity. We derive the positions of the confining intensity maxima and minima and discuss the application of the Poggendorff ring for trapping ultra-cold atoms using the repulsive dipole force of blue-detuned light. We give analytical expressions for the trapping frequencies and potential depths along both the radial and the axial directions. Finally, we present realistic numerical simulations of the dynamics of a 87Rb Bose-Einstein condensate trapped inside the Poggendorff ring which are in good agreement with corresponding experimental results.

Temperature-dependent internal quantum efficiency of blue high-brightness light-emitting diodes

Internal quantum efficiency (IQE) of a blue high-brightness InGaN/GaN light-emitting diode (LED) was evaluated from the external quantum efficiency measured as a function of current at various temperatures ranged between 13 and 440 K. Processing the data with a novel evaluation procedure based on the ABC-model, we have determined the temperature-dependent IQE of the LED structure and light extraction efficiency of the LED chip. Separate evaluation of these parameters is helpful for further optimization of the heterostructure and chip designs. The data obtained enable making a guess on the temperature dependence of the radiative and Auger recombination coefficients, which may be important for identification of dominant mechanisms responsible for the efficiency droop in III-nitride LEDs. Thermal degradation of the LED performance in terms of the emission efficiency is also considered.

Novel evaluation procedure for internal and extraction efficiency of high-power blue LEDs

Internal quantum efficiency (IQE) of a high-brightness blue LED has been evaluated from the external quantum efficiency measured as a function of current at room temperature. Processing the data with a novel evaluation procedure based on the ABC-model, we have determined separately IQE of the LED structure and light extraction efficiency (LEE) of UX:3 chip. Full text Nowadays, understanding of LED efficiency behavior at high currents is quite critical to find ways for further improve­ment of III-nitride LED performance [1]. External quantum ef­ficiency ηe (EQE) provides integral information on the recom­bination and photon emission processes in LEDs. Meanwhile EQE is the product of IQE ηi and LEE ηext at negligible car­rier leakage from the active region. Separate determination of IQE and LEE would be much more helpful, providing correla­tion between these parameters and specific epi-structure and chip design. In this paper, we extend the approach of [2,3] to the whole range of the current/optical power variation, provid­ing an express tool for separate evaluation of IQE and LEE. We studied an InGaN-based LED fabricated by Osram OS. LED structure grown by MOCVD on sapphire substrate was processed as UX:3 chip and mounted into the Golden Dragon package without molding. EQE was measured with Labsphere CDS-600 spectrometer. Plotting EQE versus output power P and finding the power Pm corresponding to EQE maximum ηm enables comparing the measurements with the analytical rela­tionships ηi = Q/(Q+p1/2+p-1/2) ,p = P/Pm , and Q = B/(AC) 1/2 where A, Band C are recombination constants [4]. As a result, maximum IQE value equal to QI(Q+2) can be found from the ratio ηm/ηe plotted as a function of p1/2 +p1-1/2 (see Fig.la) and then LEE calculated as ηext = ηm (Q+2)/Q . Experimental EQE as a function of normalized optical power p is shown in Fig. 1 b along with the analytical approximation based on the ABC­model. The approximation fits perfectly the measurements in the range of the optical power (or operating current) variation by eight orders of magnitude. In conclusion, new express method for separate evaluation of IQE and LEE of III-nitride LEDs is suggested and applied to characterization of a high-brightness blue LED. With this method, we obtained LEE from the free chip surface to the air as 69.8% and IQE as 85.7% at the maximum and 65.2% at the operation current 350 rnA. [I] G. Verzellesi, D. Saguatti, M. Meneghini, F. Bertazzi, M. Goano, G. Meneghesso, and E. Zanoni, "Efficiency droop in InGaN/GaN blue light-emitting diodes: Physical mechanisms and remedies," 1. AppL Phys., vol. 114, no. 7, pp. 071101, Aug., 2013. [2] C. van Opdorp and G. W. 't Hooft, "Method for determining effective non radiative lifetime and leakage losses in double-heterostructure las­ers," 1. AppL Phys., vol. 52, no. 6, pp. 3827-3839, Feb., 1981. [3] M. Meneghini, N. Trivellin, G. Meneghesso, E. Zanoni, U. Zehnder, and B. Hahn, "A combined electro-optical method for the determination of the recombination parameters in InGaN-based light-emitting diodes," 1. AppL Phys., vol. 106, no. II, pp. 114508, Dec., 2009. [4] Qi Dai, Qifeng Shan, ling Wang, S. Chhajed, laehee Cho, E. F. Schubert, M. H. Crawford, D. D. Koleske, Min-Ho Kim, and Yongjo Park, "Carrier recombination mechanisms and efficiency droop in GalnN/GaN light-emitting diodes," App/. Phys. Leu., vol. 97, no. 13, pp. 133507, Sept., 2010. © 2014 IEEE.