Liquid-liquid phase transition for soft-core attractive potential

Using event-driven molecular dynamics simulations, we study a three-dimensional one-component system of spherical particles interacting via a discontinuous potential combining a repulsive square soft core and an attractive square well. In the case of a narrow attractive well, it has been shown that this potential has two metastable gas-liquid critical points. Here we systematically investigate how the changes of the parameters of this potential affect the phase diagram of the system. We find a broad range of potential parameters for which the system has both a gas-liquid critical point C1 and a liquid-liquid critical point C2. For the liquid-gas critical point we find that the derivatives of the critical temperature and pressure, with respect to the parameters of the potential, have the same signs: they are positive for increasing width of the attractive well and negative for increasing width and repulsive energy of the soft core. This result resembles the behavior of the liquid-gas critical point for standard liquids. In contrast, for the liquid-liquid critical point the critical pressure decreases as the critical temperature increases. As a consequence, the liquid-liquid critical point exists at positive pressures only in a finite range of parameters. We present a modified van der Waals equation which qualitatively reproduces the behavior of both critical points within some range of parameters, and gives us insight on the mechanisms ruling the dependence of the two critical points on the potential¿s parameters. The soft-core potential studied here resembles model potentials used for colloids, proteins, and potentials that have been related to liquid metals, raising an interesting possibility that a liquid-liquid phase transition may be present in some systems where it has not yet been observed.

Juxtaposition of melt impregnation and high-temperature shear zones in the upper mantle; field and petrological constraints from the Lanzo peridotite (Northern Italy)

Results of a field and microstructural study between the northern and the central bodies of the Lanzo plagioclase peridotite massif (NW Italy) indicate that the spatial distribution of deformation is asymmetric across kilometre-scale mantle shear zones. The southwestern part of the shear zone (footwall) shows a gradually increasing degree of deformation from porphyroclastic peridotites to mylonite, whereas the northeastern part (hanging wall) quickly grades into weakly deformed peridotites. Discordant gabbroic and basaltic dykes are asymmetrically distributed and far more abundant in the footwall of the shear zone. The porphyroclastic peridotite displays porphyroclastic zones and domains of igneous crystallization whereas mylonites are characterized by elongated porphyroclasts, embedded between fine-grained, polycrystalline bands of olivine, plagioclase, clinopyroxene, orthopyroxene, spinel, rare titanian pargasite, and domains of recrystallized olivine. Two types of melt impregnation textures have been found: (1) clinopyroxene porphyroclasts incongruently reacted with migrating melt to form orthopyroxene plagioclase; (2) olivine porphyroclasts are partially replaced by interstitial orthopyroxene. The meltrock reaction textures tend to disappear in the mylonites, indicating that deformation in the mylonite continued under subsolidus conditions. The pyroxene chemistry is correlated with grain size. High-Al pyroxene cores indicate high temperatures (11001030C), whereas low-Al neoblasts display lower final equilibration temperatures (860C). The spinel Cr-number [molar Cr/(Cr Al)] and TiO2 concentrations show extreme variability covering almost the entire range known from abyssal peridotites. The spinel compositions of porphyroclastic peridotites from the central body are more variable than spinel from mylonite, mylonite with ultra-mylonite bands, and porphyroclastic rocks of the northern body. The spinel compositions probably indicate disequilibrium and would favour rapid cooling, and a faster exhumation of the central peridotite body, relative to the northern one. Our results indicate that melt migration and high-temperature deformation are juxtaposed both in time and space. Meltrock reaction may have caused grain-size reduction, which in turn led to localization of deformation. It is likely that melt-lubricated, actively deforming peridotites acted as melt focusing zones, with permeabilities higher than the surrounding, less deformed peridotites. Later, under subsolidus conditions, pinning in polycrystalline bands in the mylonites inhibited substantial grain growth and led to permanent weak zones in the upper mantle peridotite, with a permeability that is lower than in the weakly deformed peridotites. Such an inversion in permeability might explain why actively deforming, fine-grained peridotite mylonite acted as a permeability barrier and why ascending mafic melts might terminate and crystallize as gabbros along actively deforming shear zones. Melt-lubricated mantle shear zones provide a mechanism for explaining the discontinuous distribution of gabbros in oceancontinent transition zones, oceanic core complexes and ultraslow-spreading ridges.

Real-time monitoring of the silicidation process of tungsten filaments at high temperature used as catalysers for silane decomposition

The scope of this work is the systematic study of the silicidation process affecting tungsten filaments at high temperature (1900ºC) used for silane decomposition in the hot-wire chemical vapour deposition technique (HWCVD). The correlation between the electrical resistance evolution of the filaments, Rfil(t), and the different stages of the their silicidation process is exposed. Said stages correspond to: the rapid formation of two WSi2 fronts at the cold ends of the filaments and their further propagation towards the middle of the filaments; and, regarding the hot central portion of the filaments: a initial stage of silicon dissolution into the tungsten bulk, with a random duration for as-manufactured filaments, followed by the inhomogeneous nucleation of W5Si3 (which is later replaced by WSi2) and its further growth towards the filaments core. An electrical model is used to obtain real-time information about the current status of the filaments silicidation process by simply monitoring their Rfil(t) evolution during the HWCVD process. It is shown that implementing an annealing pre-treatment to the filaments leads to a clearly repetitive trend in the monitored Rfil(t) signatures. The influence of hydrogen dilution of silane on the filaments silicidation process is also discussed.

Heat Transfer Analysis of the EPR Core Catcher Test Facility Volley

Uusi EPR-reaktorikonsepti on suunniteltu selviytymään tapauksista, joissa reaktorinsydän sulaa ja sula puhkaisee paineastian. Suojarakennuksen sisälle on suunniteltu alue, jolle sula passiivisesti kerätään, pidätetään ja jäähdytetään. Alueelle laaditaan valurautaelementeistä ns.sydänsieppari, joka tulvitetaan vedellä. Sydänsulan tuottama jälkilämpö siirtyyveteen, mistä se poistetaan suojarakennuksen jälkilämmönpoistojärjestelmän kautta. Suuri osa lämmöstä poistuu sydänsulasta sen yläpuolella olevaan veteen, mutta lämmönsiirron tehostamiseksi myös sydänsiepparin alapuolelle on sijoitettu vedellä täytettävät jäähdytyskanavat. Jotta sydänsiepparin toiminta voitaisiin todentaa, on Lappeenrannan Teknillisellä Yliopistolla rakennettu Volley-koelaitteisto tätä tarkoitusta varten. Koelaitteisto koostuu kahdesta täysimittaisesta valuraudasta tehdystä jäähdytyskanavasta. Sydänsulan tuottamaa jälkilämpöä simuloidaan koelaitteistossa sähkövastuksilla. Tässä työssä kuvataan simulaatioiden suorittaminen ja vertaillaan saatuja arvoja mittaustuloksiin. Työ keskittyy sydänsiepparista jäähdytyskanaviin tapahtuvan lämmönsiirron teoriaan jamekanismeihin. Työssä esitetään kolme erilaista korrelaatiota lämmönsiirtokertoimille allaskiehumisen tapauksessa. Nämä korrelaatiot soveltuvat erityisesti tapauksiin, joissa vain muutamia mittausparametreja on tiedossa. Työn toinen osa onVolley 04 -kokeiden simulointi. Ensin käytettyä simulointitapaa on kelpoistettuvertaamalla tuloksia Volley 04 ja 05 -kokeisiin, joissa koetta voitiin jatkaa tasapainotilaan ja joissa jäähdytteen käyttäytyminen jäähdytyskanavassa on tallennettu myös videokameralla. Näiden simulaatioiden tulokset ovat hyvin samanlaisiakuin mittaustulokset. Korkeammilla lämmitystehoilla kokeissa esiintyi vesi-iskuja, jotka rikkoivat videoinnin mahdollistavia ikkunoita. Tämän johdosta osassa Volley 04 -kokeita ikkunat peitettiin metallilevyillä. Joitakin kokeita jouduttiin keskeyttämään laitteiston suurten lämpöjännitysten johdosta. Tällaisten testien simulaatiot eivät ole yksinkertaisia suorittaa. Veden pinnan korkeudesta ei ole visuaalista havaintoa. Myöskään jäähdytteen tasapainotilanlämpötiloista ei ole tarkkaa tietoa, mutta joitakin oletuksia voidaan tehdä samoilla parametreilla tehtyjen Volley 05 -kokeiden perusteella. Mittaustulokset Volley 04 ja 05 -kokeista, jotka on videoitu ja voitu ajaa tasapainotilaan saakka, antoivat simulaatioiden kanssa hyvin samankaltaisia lämpötilojen arvoja. Keskeytettyjen kokeiden ekstrapolointi tasapainotilaan ei onnistunut kovin hyvin. Kokeet jouduttiin keskeyttämään niin paljon ennen termohydraulista tasapainoa, ettei tasapainotilan reunaehtoja voitu ennustaa. Videonauhoituksen puuttuessa ei veden pinnan korkeudesta saatu lisätietoa. Tuloksista voidaan lähinnä esittää arvioita siitä, mitä suuruusluokkaa mittapisteiden lämpötilat tulevat olemaan. Nämä lämpötilat ovat kuitenkin selvästi alle sydänsiepparissa käytettävän valuraudan sulamislämpötilan. Joten simulaatioiden perusteella voidaan sanoa, etteivät jäähdytyskanavien rakenteet sula, mikäli niissä on pienikin jäähdytevirtaus, eikä useampia kuin muutama vierekkäinen kanava ole täysin kuivana.

Differential regulation of horizontally acquired and core genome genes by the bacterial modulator H-NS

Horizontal acquisition of DNA by bacteria dramatically increases genetic diversity and hence successful bacterial colonization of several niches, including the human host. A relevant issue is how this newly acquired DNA interacts and integrates in the regulatory networks of the bacterial cell. The global modulator H-NS targets both core genome and HGT genes and silences gene expression in response to external stimuli such as osmolarity and temperature. Here we provide evidence that H-NS discriminates and differentially modulates core and HGT DNA. As an example of this, plasmid R27-encoded H-NS protein has evolved to selectively silence HGT genes and does not interfere with core genome regulation. In turn, differential regulation of both gene lineages by resident chromosomal H-NS requires a helper protein: the Hha protein. Tight silencing of HGT DNA is accomplished by H-NS-Hha complexes. In contrast, core genes are modulated by H-NS homoligomers. Remarkably, the presence of Hha-like proteins is restricted to the Enterobacteriaceae. In addition, conjugative plasmids encoding H-NS variants have hitherto been isolated only from members of the family. Thus, the H-NS system in enteric bacteria presents unique evolutionary features. The capacity to selectively discriminate between core and HGT DNA may help to maintain horizontally transmitted DNA in silent form and may give these bacteria a competitive advantage in adapting to new environments, including host colonization.

Differential regulation of horizontally acquired and core genome genes by the bacterial modulator H-NS

Horizontal acquisition of DNA by bacteria dramatically increases genetic diversity and hence successful bacterial colonization of several niches, including the human host. A relevant issue is how this newly acquired DNA interacts and integrates in the regulatory networks of the bacterial cell. The global modulator H-NS targets both core genome and HGT genes and silences gene expression in response to external stimuli such as osmolarity and temperature. Here we provide evidence that H-NS discriminates and differentially modulates core and HGT DNA. As an example of this, plasmid R27-encoded H-NS protein has evolved to selectively silence HGT genes and does not interfere with core genome regulation. In turn, differential regulation of both gene lineages by resident chromosomal H-NS requires a helper protein: the Hha protein. Tight silencing of HGT DNA is accomplished by H-NS-Hha complexes. In contrast, core genes are modulated by H-NS homoligomers. Remarkably, the presence of Hha-like proteins is restricted to the Enterobacteriaceae. In addition, conjugative plasmids encoding H-NS variants have hitherto been isolated only from members of the family. Thus, the H-NS system in enteric bacteria presents unique evolutionary features. The capacity to selectively discriminate between core and HGT DNA may help to maintain horizontally transmitted DNA in silent form and may give these bacteria a competitive advantage in adapting to new environments, including host colonization.

Coolant Flow and Heat Transfer in Pebble-Bed Reactor Core

This thesis gathers knowledge about ongoing high-temperature reactor projects around the world. Methods for calculating coolant flow and heat transfer inside a pebble-bed reactor core are also developed. The thesis begins with the introduction of high-temperature reactors including the current state of the technology. Process heat applications that could use the heat from a high-temperature reactor are also introduced. A suitable reactor design with data available in literature is selected for the calculation part of the thesis. Commercial computational fluid dynamics software Fluent is used for the calculations. The pebble-bed is approximated as a packed-bed, which causes sink terms to the momentum equations of the gas flowing through it. A position dependent value is used for the packing fraction. Two different models are used to calculate heat transfer. First a local thermal equilibrium is assumed between the gas and solid phases and a single energy equation is used. In the second approach, separate energy equations are used for the phases. Information about steady state flow behavior, pressure loss, and temperature distribution in the core is obtained as results of the calculations. The effect of inlet mass flow rate to pressure loss is also investigated. Data found in literature and the results correspond each other quite well, considered the amount of simplifications in the calculations. The models developed in this thesis can be used to solve coolant flow and heat transfer in a pebble-bed reactor, although additional development and model validation is needed for better accuracy and reliability.

Pressure Drop in Vertical Core-Annular Flow

An experimental apparatus for the study of core annular flows of heavy oil and water at room temperature has been set up and tested at laboratory scale. The test section consists of a 2.75 cm ID galvanized steel pipe. Tap water and a heavy oil (17.6 Pa.s; 963 kg/m³) were used. Pressure drop in a vertical upward test section was accurately measured for oil flow rates in the range 0.297 - 1.045 l/s and water flow rates ranging from 0.063 to 0.315 l/s. The oil-water input ratio was in the range 1-14. The measured pressure drop comprises gravitational and frictional parts. The gravitational pressure drop was expressed in terms of the volumetric fraction of the core, which was determined from a correlation developed by Bannwart (1998b). The existence of an optimum water-oil input ratio for each oil flow rate was observed in the range 0.07 - 0.5. The frictional pressure drop was modeled to account for both hydrodynamic and net buoyancy effects on the core. The model was adjusted to fit our data and shows excellent agreement with data from another source (Bai, 1995).

Manifestation of the pairing symmetry in the vortex core structure in iron-based superconductors

The superconducting gap is a basic character of a superconductor. While the cuprates and conventional phonon-mediated superconductors are characterized by distinct d- and s-wave pairing symmetries with nodal and nodeless gap distributions respectively, the superconducting gap distributions in iron-based superconductors are rather diversified. While nodeless gap distributions have been directly observed in Ba1–xKxFe2As2, BaFe2–xCoxAs2, LiFeAs, KxFe2–ySe2, and FeTe1–xSex, the signatures of a nodal superconducting gap have been reported in LaOFeP, LiFeP, FeSe, KFe2As2, BaFe2–xRuxAs2, and BaFe2(As1–xPx)2. Due to the multiplicity of the Fermi surface in these compounds s± and d pairing states can be both nodeless and nodal. A nontrivial orbital structure of the order parameter, in particular the presence of the gap nodes, leads to effects in which the disorder is much richer in dx2–y2-wave superconductors than in conventional materials. In contrast to the s-wave case, the Anderson theorem does not work, and nonmagnetic impurities exhibit a strong pair-breaking influence. In addition, a finite concentration of disorder produces a nonzero density of quasiparticle states at zero energy, which results in a considerable modification of the thermodynamic and transport properties at low temperatures. The influence of order parameter symmetry on the vortex core structure in iron-based pnictide and chalcogenide superconductors has been investigated in the framework of quasiclassical Eilenberger equations. The main results of the thesis are as follows. The vortex core characteristics, such as, cutoff parameter, ξh, and core size, ξ2, determined as the distance at which density of the vortex supercurrent reaches its maximum, are calculated in wide temperature, impurity scattering rate, and magnetic field ranges. The cutoff parameter, ξh(B; T; Г), determines the form factor of the flux-line lattice, which can be obtained in _SR, NMR, and SANS experiments. A comparison among the applied pairing symmetries is done. In contrast to s-wave systems, in dx2–y2-wave superconductors, ξh/ξc2 always increases with the scattering rate Г. Field dependence of the cutoff parameter affects strongly on the second moment of the magnetic field distributions, resulting in a significant difference with nonlocal London theory. It is found that normalized ξ2/ξc2(B/Bc2) dependence is increasing with pair-breaking impurity scattering (interband scattering for s±-wave and intraband impurity scattering for d-wave superconductors). Here, ξc2 is the Ginzburg-Landau coherence length determined from the upper critical field Bc2 = Φ0/2πξ2 c2, where Φ0 is a flux quantum. Two types of ξ2/ξc2 magnetic field dependences are obtained for s± superconductors. It has a minimum at low temperatures and small impurity scattering transforming in monotonously decreasing function at strong scattering and high temperatures. The second kind of this dependence has been also found for d-wave superconductors at intermediate and high temperatures. In contrast, impurity scattering results in decreasing of ξ2/ξc2(B/Bc2) dependence in s++ superconductors. A reasonable agreement between calculated ξh/ξc2 values and those obtained experimentally in nonstoichiometric BaFe2–xCoxAs2 (μSR) and stoichiometric LiFeAs (SANS) was found. The values of ξh/ξc2 are much less than one in case of the first compound and much more than one for the other compound. This is explained by different influence of two factors: the value of impurity scattering rate and pairing symmetry.

Thermal-Aware Networked Many-Core Systems

Advancements in IC processing technology has led to the innovation and growth happening in the consumer electronics sector and the evolution of the IT infrastructure supporting this exponential growth. One of the most difficult obstacles to this growth is the removal of large amount of heatgenerated by the processing and communicating nodes on the system. The scaling down of technology and the increase in power density is posing a direct and consequential effect on the rise in temperature. This has resulted in the increase in cooling budgets, and affects both the life-time reliability and performance of the system. Hence, reducing on-chip temperatures has become a major design concern for modern microprocessors. This dissertation addresses the thermal challenges at different levels for both 2D planer and 3D stacked systems. It proposes a self-timed thermal monitoring strategy based on the liberal use of on-chip thermal sensors. This makes use of noise variation tolerant and leakage current based thermal sensing for monitoring purposes. In order to study thermal management issues from early design stages, accurate thermal modeling and analysis at design time is essential. In this regard, spatial temperature profile of the global Cu nanowire for on-chip interconnects has been analyzed. It presents a 3D thermal model of a multicore system in order to investigate the effects of hotspots and the placement of silicon die layers, on the thermal performance of a modern ip-chip package. For a 3D stacked system, the primary design goal is to maximise the performance within the given power and thermal envelopes. Hence, a thermally efficient routing strategy for 3D NoC-Bus hybrid architectures has been proposed to mitigate on-chip temperatures by herding most of the switching activity to the die which is closer to heat sink. Finally, an exploration of various thermal-aware placement approaches for both the 2D and 3D stacked systems has been presented. Various thermal models have been developed and thermal control metrics have been extracted. An efficient thermal-aware application mapping algorithm for a 2D NoC has been presented. It has been shown that the proposed mapping algorithm reduces the effective area reeling under high temperatures when compared to the state of the art.

Association between the increase in brain temperature and physical performance at different exercise intensities and protocols in a temperate environment

There is evidence that brain temperature (Tbrain) provides a more sensitive index than other core body temperatures in determining physical performance. However, no study has addressed whether the association between performance and increases in Tbrain in a temperate environment is dependent upon exercise intensity, and this was the primary aim of the present study. Adult male Wistar rats were subjected to constant exercise at three different speeds (18, 21, and 24 m/min) until the onset of volitional fatigue. Tbrain was continuously measured by a thermistor inserted through a brain guide cannula. Exercise induced a speed-dependent increase in Tbrain, with the fastest speed associated with a higher rate of Tbrain increase. Rats subjected to constant exercise had similar Tbrain values at the time of fatigue, although a pronounced individual variability was observed (38.7-41.7°C). There were negative correlations between the rate of Tbrain increase and performance for all speeds that were studied. These results indicate that performance during constant exercise is negatively associated with the increase in Tbrain, particularly with its rate of increase. We then investigated how an incremental-speed protocol affected the association between the increase in Tbrain and performance. At volitional fatigue, Tbrain was lower during incremental exercise compared with the Tbrain resulting from constant exercise (39.3±0.3 vs 40.3±0.1°C; P<0.05), and no association between the rate of Tbrain increase and performance was observed. These findings suggest that the influence of Tbrain on performance under temperate conditions is dependent on exercise protocol.

Energy aware software for many-core systems

Many-core systems provide a great potential in application performance with the massively parallel structure. Such systems are currently being integrated into most parts of daily life from high-end server farms to desktop systems, laptops and mobile devices. Yet, these systems are facing increasing challenges such as high temperature causing physical damage, high electrical bills both for servers and individual users, unpleasant noise levels due to active cooling and unrealistic battery drainage in mobile devices; factors caused directly by poor energy efficiency. Power management has traditionally been an area of research providing hardware solutions or runtime power management in the operating system in form of frequency governors. Energy awareness in application software is currently non-existent. This means that applications are not involved in the power management decisions, nor does any interface between the applications and the runtime system to provide such facilities exist. Power management in the operating system is therefore performed purely based on indirect implications of software execution, usually referred to as the workload. It often results in over-allocation of resources, hence power waste. This thesis discusses power management strategies in many-core systems in the form of increasing application software awareness of energy efficiency. The presented approach allows meta-data descriptions in the applications and is manifested in two design recommendations: 1) Energy-aware mapping 2) Energy-aware execution which allow the applications to directly influence the power management decisions. The recommendations eliminate over-allocation of resources and increase the energy efficiency of the computing system. Both recommendations are fully supported in a provided interface in combination with a novel power management runtime system called Bricktop. The work presented in this thesis allows both new- and legacy software to execute with the most energy efficient mapping on a many-core CPU and with the most energy efficient performance level. A set of case study examples demonstrate realworld energy savings in a wide range of applications without performance degradation.

Pigment orientation changes detected by low temperature linear dichroism spectroscopy: cold-hardening transition in phycobilisome-containing organisms

Low temperature (77K) linear dichroism spectroscopy was used to characterize pigment orientation changes accompanying the light state transition in the cyanobacterium, Synechococcus sp. pee 6301, and cold-hardening in winter rye (Secale cereale L. cv. Puma). Samples were oriented for spectroscopy using the gel squeezing method (Abdourakhmanov et aI., 1979) and brought to 77K in liquid nitrogen. The linear dichroism (LD) spectra of Synechococcus 6301 phycobilisome/thylakoid membrane fragments cross-linked in light state 1 and light state 2 with glutaraldehyde showed differences in both chlorophyll a and phycobilin orientation. A decrease in the relative amplitude of the 681nm chlorophyll a positive LD peak was observed in membrane fragments in state 2. Reorientation of the phycobilisome (PBS) during the transition to state 2 resulted in an increase in core allophycocyanin absorption parallel to the membrane, and a decrease in rod phycocyanin parallel absorption. This result supports the "spillover" and "PBS detachment" models of the light state transition in PBS-containing organisms, but not the "mobile PBS" model. A model was proposed for PBS reorientation upon transition to state 2, consisting of a tilt in the antenna complex with respect to the membrane plane. Linear dichroism spectra of PBS/thylakoid fragments from the red alga, Porphyridium cruentum, grown in green light (containing relatively more PSI) and red light (containing relatively more PSll) were compared to identify chlorophyll a absorption bands associated with each photosystem. Spectra from red light - grown samples had a larger positive LD signal on the short wavelength side of the 686nm chlorophyll a peak than those from green light - grown fragments. These results support the identification of the difference in linear dichroism seen at 681nm in Synechococcus spectra as a reorientation of PSll chromophores. Linear dichroism spectra were taken of thylakoid membranes isolated from winter rye grown at 20°C (non-hardened) and 5°C (cold-hardened). Differences were seen in the orientation of chlorophyll b relative to chlorophyll a. An increase in parallel absorption was identified at the long-wavelength chlorophyll a absorption peak, along with a decrease in parallel absorption from chlorophyll b chromophores. The same changes in relative pigment orientation were seen in the LD of isolated hardened and non-hardened light-harvesting antenna complexes (LHCII). It was concluded that orientational differences in LHCII pigments were responsible for thylakoid LD differences. Changes in pigment orientation, along with differences observed in long-wavelength absorption and in the overall magnitude of LD in hardened and non-hardened complexes, could be explained by the higher LHCII monomer:oligomer ratio in hardened rye (Huner et ai., 1987) if differences in this ratio affect differential light scattering properties, or fluctuation of chromophore orientation in the isolated LHCII sample.

A new emissive Ru(II)N5O core

From the reaction of cis-Ru(1,10-phenanthroline)(2)Cl(2 center dot)2H(2)O with 2-picolinic acid in 1:1 molar ratio in degassed methanol-water mixture, [Ru(1,10-phenanthroline)(2)(2-picolinate)]PF6 center dot H2O (1) has been isolated as a red compound by adding excess of NH4PF6. Single crystal X-ray crystallography shows that the metal in 1 has an octahedral N5O coordination sphere. Complex 1 displays (MLCT)-M-1 bands in the 400-500 nm region in acetonitrile. Upon excitation at 435 nm, complex 1 gives rise to a broad emission band at 675 nm in acetonitrile at room temperature with a quantum yield of 0.0022. The energy of the MLCT state in 1 is estimated as 1.99 eV. Since, from cyclic voltammetry, the ground state potential of the Ru(II/III) couple in 1 is found to be 1.01 V vs NHE, the potential of the same couple in the excited state is calculated as -0.98 V vs NHE. The emissive state in 1 seems to be the triplet Ru(II) -> 1, 10-phenanthroline charge transfer state.

A fluxional (CuN2O2)-N-I core: binding of a keto oxygen atom to Cu-I and Ag-I

[Cu(2-acetylpyridine)(2)]ClO4 (1), characterised here, has a novel Cu'N202 core in the solid state. Variable-temperature H-1 NMR studies show that the two chelate rings open up in solution at room temperature and the keto oxygen atoms dangle freely. As the temperature is lowered, the 0 atoms tend to bind to the metal atom. The corresponding silver(I) complex, [Ag(2-acetylpyridine)2]ClO4 (4), characterised by single-crystal X-ray crystallography, has an (AgN2)-N-I core in the solid state as well as in solution. Thus, while 1 is fluxional, 4 is not. In cyclic voltammetry, complex 1 displays a quasireversible Cu-II/I couple with a half-wave potential of 0.40 V vs. SCE. Complex I is easily oxidised by air and H2O2 in methanol to give rise to a dinuclear copper(II) complex where the ligand framework is not simple acetylpyridine. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).