On the strong uniqueness of some finite dimensional Dirichlet operators

We prove essential self-adjointness of a class of Dirichlet operators in ℝn using the hyperbolic equation approach. This method allows one to prove essential self-adjointness under minimal conditions on the logarithmic derivative of the density and a condition of Muckenhoupt type on the density itself.

Unusual isotope effect in the reaction of chlorosilylene with trimethylsilane-1-d: Absolute rate studies and quantum chemical and Rice–Ramsperger–Kassel–Marcus calculations provide strong evidence for the involvement of an intermediate complex

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1- silacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with trimethylsilane-1-d, Me3SiD, in the gas phase. The reaction was studied at total pressures up to 100 Torr (with and without added SF6) over the temperature range of 295−407 K. The rate constants were found to be pressure independent and gave the following Arrhenius equation: log[(k/(cm3 molecule−1 s−1)] = (−13.22 ± 0.15) + [(13.20 ± 1.00) kJ mol−1]/(RT ln 10). When compared with previously published kinetic data for the reaction of ClSiH with Me3SiH, kinetic isotope effects, kD/kH, in the range from 7.4 (297 K) to 6.4 (407 K) were obtained. These far exceed values of 0.4−0.5 estimated for a single-step insertion process. Quantum chemical calculations (G3MP2B3 level) confirm not only the involvement of an intermediate complex, but also the existence of a low-energy internal isomerization pathway which can scramble the D and H atom labels. By means of Rice−Ramsperger−Kassel−Marcus modeling and a necessary (but small) refinement of the energy surface, we have shown that this mechanism can reproduce closely the experimental isotope effects. These findings provide the first experimental evidence for the isomerization pathway and thereby offer the most concrete evidence to date for the existence of intermediate complexes in the insertion reactions of silylenes.

Insertion of a hydroxido bridge into a diphenoxido dinuclear copper(II) complex: drastic change of the magnetic property from strong antiferromagnetic to ferromagnetic and enhancement in the catecholase activity

A diphenoxido-bridged dinuclear copper(II) complex, [Cu2L2(ClO4)(2)] (1), has been synthesized using a tridentate reduced Schiff base ligand, 2-[[2-(diethylamino)-ethylamino]methyl]phenol (HL). The addition of triethylamine to the methanolic solution of this complex produced a novel triple bridged (double phenoxido and single hydroxido) dinuclear copper(II) complex, [Cu2L2(OH)]ClO4 (2). Both complexes 1 and 2 were characterized by X-ray structural analyses, variable-temperature magnetic susceptibility measurements, and spectroscopic methods. In 1, the two phenoxido bridges are equatorial-equatorial and the species shows strong antiferromagnetic coupling with J = -615.6(6.1) cm(-1). The inclusion of the equatorial-equatorial hydroxido bridge in 2 changes the Cu center dot center dot center dot Cu distance from 3.018 angstrom (avg.) to 2.798 angstrom (avg.), the positions of the phenoxido bridges to axial-equatorial, and the magnetic coupling to ferromagnetic with J = 50.1(1.4) cm(-1). Using 3,5-di-tert-butylcatechol as the substrate, the catecholase activity of the complexes has been studied in a methanol solution; compound 2 shows higher catecholase activity (k(cat) = 233.4 h(-1)) than compound 1 (k(cat) = 93.6 h(-1)). Both complexes generate identical species in solution, and they are interconvertible simply by changing the pH of their solutions. The higher catecholase activity of 2 seems to be due to the presence of the OH group, which increases the pH of its solution.

Strong structural controllability and the multilink inverted pendulum

This technical note investigates the controllability of the linearized dynamics of the multilink inverted pendulum as the number of links and the number and location of actuators changes. It is demonstrated that, in some instances, there exist sets of parameter values that render the system uncontrollable and so usual methods for assessing controllability are difficult to employ. To assess the controllability, a theorem on strong structural controllability for single-input systems is extended to the multiinput case.

On the development of strong ridge episodes over the eastern North Atlantic

The occurrence of strong and persistent mid-latitude anticyclonic ridges over the Eastern North Atlantic is a major contributor to the occurrence of severe winter droughts over Western Iberia. We analyze the development of strong and persistent ridge episodes within 40–50°N; 40°W–5°E, which are defined as 300 hPa geopotential height anomalies above 50 gpm that persist for at least 10 consecutive days. Results suggest that the generation and maintenance of these episodes, with positive stratospheric geopotential anomalies over the North American continent and the adjacent North Pacific, are associated with an intensified polar jet. Such positive anomalies tend to detach from the main stratospheric anomaly and propagate eastwards and downwards as Rossby tropospheric waves. Furthermore, the Eastern North Atlantic ridge is generated and repeatedly reinforced until the stratospheric anomaly dissipates. Results also show evidence for waves breaking anticyclonically during the episodes, which is dynamically coherent with their persistency and quasi-stationarity.

Impact of strong deep ocean stratification on the glacial carbon cycle

During the Last Glacial Maximum, the climate was substantially colder and the carbon cycle was clearly different from the late Holocene. According to proxy data deep oceanic δ13C was very low, and the atmospheric CO2 concentration also reduced. Several mechanisms have been proposed to explain these changes, but none can fully explain the data, especially the very low deep ocean δ13C values. Oceanic core data show that the deep ocean was very cold and salty, which would lead to enhanced deep ocean stratification. We show that such an enhanced stratification in the coupled climate model CLIMBER-2 helps get very low deep oceanic δ13C values. Indeed the simulated δ13C reaches values as low as −0.8‰ in line with proxy data evidences. Moreover it increases the oceanic carbon reservoir leading to a small, yet robust, atmospheric CO2 drop of approximately 10 ppm.

Strong armies, slow adaptation: civil-military relations and diffusion of military power

Why are some states more willing to adopt military innovations than others? Why, for example, were the great powers of Europe able to successfully reform their military practices to better adapt to and participate in the so-called military revolution of the sixteenth and seventeenth centuries while their most important extra-European competitor, the Ottoman Empire, failed to do so? This puzzle is best explained by two factors: civil-military relations and historical timing. In the Ottoman Empire, the emergence of an institutionally strong and internally cohesive army during the early stages of state formation—in the late fourteenth century—equipped the military with substantial bargaining powers. In contrast, the great powers of Europe drew heavily on private providers of military power during the military revolution and developed similar armies only by the second half of the seventeenth century, limiting the bargaining leverage of European militaries over their rulers. In essence, the Ottoman standing army was able to block reform efforts that it believed challenged its parochial interests. Absent a similar institutional challenge, European rulers initiated military reforms and motivated officers and military entrepreneurs to participate in the ongoing military revolution.

Observations of urban boundary layer structure during a strong urban heat island event

It has long been known that the urban surface energy balance is different to that of a rural surface, and that heating of the urban surface after sunset gives rise to the Urban Heat Island (UHI). Less well known is how flow and turbulence structure above the urban surface are changed during different phases of the urban boundary layer (UBL). This paper presents new observations above both an urban and rural surface and investigates how much UBL structure deviates from classical behaviour. A 5-day, low wind, cloudless, high pressure period over London, UK, was chosen for analysis, during which there was a strong UHI. Boundary layer evolution for both sites was determined by the diurnal cycle in sensible heat flux, with an extended decay period of approximately 4 h for the convective UBL. This is referred to as the “Urban Convective Island” as the surrounding rural area was already stable at this time. Mixing height magnitude depended on the combination of regional temperature profiles and surface temperature. Given the daytime UHI intensity of 1.5∘C, combined with multiple inversions in the temperature profile, urban and rural mixing heights underwent opposite trends over the period, resulting in a factor of three height difference by the fifth day. Nocturnal jets undergoing inertial oscillations were observed aloft in the urban wind profile as soon as the rural boundary layer became stable: clear jet maxima over the urban surface only emerged once the UBL had become stable. This was due to mixing during the Urban Convective Island reducing shear. Analysis of turbulent moments (variance, skewness and kurtosis) showed “upside-down” boundary layer characteristics on some mornings during initial rapid growth of the convective UBL. During the “Urban Convective Island” phase, turbulence structure still resembled a classical convective boundary layer but with some influence from shear aloft, depending on jet strength. These results demonstrate that appropriate choice of Doppler lidar scan patterns can give detailed profiles of UBL flow. Insights drawn from the observations have implications for accuracy of boundary conditions when simulating urban flow and dispersion, as the UBL is clearly the result of processes driven not only by local surface conditions but also regional atmospheric structure.

Beyond the environmentalist's paradox and the debate on weak versus strong sustainability

Environmentalists generally argue that ecological damage will (eventually) lead to declines in human well-being. From this perspective, the recent introduction of the “environmentalist’s paradox” in BioScience by Raudsepp-Hearne and colleagues (2010) is particularly significant. In essence, Raudsepp-Hearne and colleagues (2010) claimed that although ecosystem services have been degraded, human well-being—paradoxically—has increased. In this article, we show that this debate is in fact rooted in a broader discussion on weak sustainability versus strong sustainability(the substitutability of human-made capital for natural capital). We warn against the reductive nature of focusing only on a stock–flow framework in which a natural-capital stock produces ecosystem services. Concretely, we recommend a holistic approach in which the complexity, irreversibility, uncertainty, and ethical predicaments intrinsic to the natural environment and its connections to humanity are also considered.

Ionospheric convection response to slow, strong variations in a northward interplanetary magnetic field: A case study for January 14, 1988

We analyze ionospheric convection patterns over the polar regions during the passage of an interplanetary magnetic cloud on January 14, 1988, when the interplanetary magnetic field (IMF) rotated slowly in direction and had a large amplitude. Using the assimilative mapping of ionospheric electrodynamics (AMIE) procedure, we combine simultaneous observations of ionospheric drifts and magnetic perturbations from many different instruments into consistent patterns of high-latitude electrodynamics, focusing on the period of northward IMF. By combining satellite data with ground-based observations, we have generated one of the most comprehensive data sets yet assembled and used it to produce convection maps for both hemispheres. We present evidence that a lobe convection cell was embedded within normal merging convection during a period when the IMF By and Bz components were large and positive. As the IMF became predominantly northward, a strong reversed convection pattern (afternoon-to-morning potential drop of around 100 kV) appeared in the southern (summer) polar cap, while convection in the northern (winter) hemisphere became weak and disordered with a dawn-to-dusk potential drop of the order of 30 kV. These patterns persisted for about 3 hours, until the IMF rotated significantly toward the west. We interpret this behavior in terms of a recently proposed merging model for northward IMF under solstice conditions, for which lobe field lines from the hemisphere tilted toward the Sun (summer hemisphere) drape over the dayside magnetosphere, producing reverse convection in the summer hemisphere and impeding direct contact between the solar wind and field lines connected to the winter polar cap. The positive IMF Bx component present at this time could have contributed to the observed hemispheric asymmetry. Reverse convection in the summer hemisphere broke down rapidly after the ratio |By/Bz| exceeded unity, while convection in the winter hemisphere strengthened. A dominant dawn-to-dusk potential drop was established in both hemispheres when the magnitude of By exceeded that of Bz, with potential drops of the order of 100 kV, even while Bz remained northward. The later transition to southward Bz produced a gradual intensification of the convection, but a greater qualitative change occurred at the transition through |By/Bz| = 1 than at the transition through Bz = 0. The various convection patterns we derive under northward IMF conditions illustrate all possibilities previously discussed in the literature: nearly single-cell and multicell, distorted and symmetric, ordered and unordered, and sunward and antisunward.