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61.
We make the link between the size-dependent phase stability of a nanocrystal and the phase-transition behavior of emerging crystallites during the earliest stages of crystallization, by using the former as a proxy for the latter. We outline an extension of the classical nucleation theory to describe crystal nucleation and subsequent transformations of competing polymorphic phases that characterize Ostwald's rule of stages. The theoretical framework reveals that the relative stability of the competing phases is a function of cluster size, which in turn varies with time, and therefore explains the complex transformation behavior observed for some systems. We investigated the stability of a nanocrystal of dl-norleucine by means of molecular simulation as a proxy for post-nucleation phase-transformation behavior in emerging crystallites. The simulations reveal that, for nanocrystals, the surface energy of the transition state of a transformation can dominate the barrier to phase change, thus causing metastable phases to be stabilized, not because they are thermodynamically stable, but rather due to kinetic hindering. Therefore, in the context of the earliest stages of crystal growth, not only does phase stability vary as a function of cluster size, and hence time, but thermodynamically feasible transformations are also prone to kinetic hindering. 相似文献
62.
Tandon SS Dul MC Lee JL Dawe LN Anwar MU Thompson LK 《Dalton transactions (Cambridge, England : 2003)》2011,40(14):3466-3475
Ligands based on carbo- and thio-carbohydrazone cores, modified with pyridine, carboxylate and oxime ends, have been examined. They display a tautomeric versatility based on the flexible nature of the hydrazone linkages, leading to varied coordination motifs. Examples of mononuclear (Co(II), Ni(II)), dinuclear (Co(III)), 1D chain (Cu(II)) and square [2 × 2] grid (Ni(II)) complexes are obtained. Ferromagnetic (Cu(II)) and antiferromagnetic (Ni(II)) exchange is observed, with spin coupling in the Ni(II)(4) square grids propagated through the μ-O and μ-S bridges. Weak antiferromagnetic exchange (J = -6.0 cm(-1)) is observed for the μ-O bridged grid, despite the large Ni-O-Ni angles (137-141°), while for the μ-S bridged grids much stronger exchange is observed (J = -148 cm(-1), -198 cm(-1)). This is much larger than expected based on the Ni-S-Ni bridge angles (151-169°), and is associated with the soft (less polarizing than oxygen) nature of the sulfur bridge, which would allow for much more efficient transmission of spin exchange than observed in the μ-O bridged case. Structures and variable temperature magnetic data are included, and spin exchange is analyzed using normal Heisenberg exchange models. No examples involving oxime (NO) bridging are reported, which reflects the positioning of the N,O and N,S donor combinations in each ligand, and the preferred coordination through these donor atoms. 相似文献
63.
Abd El-Moneim Anwar Mohamed Mohamed Abd El-Hady Kassem Mohamed Abd Allah El-Hadidy 《Applied Mathematical Modelling》2011,35(9):4127-4139
This paper investigates a search problem for a brownian target motion on one of n-intersected real lines in which any information of the target position is not available to the searchers all the time. We have n-searchers start searching for the target from the origin that is the intersection point of these lines. Each of the searchers moves continuously along his line in both directions of the starting point. The purpose of this paper is to formulate a search model and find the condition under which the expected value of the first meeting time between one of the searchers and the target is finite. Also, we show the existence of the optimal search plan which minimizes the expected value of the first meeting time and find it. 相似文献
64.
Journal of Algebraic Combinatorics - We show that the $$\gamma $$ -vector of the interval subdivision of a simplicial complex with a nonnegative and symmetric h-vector is nonnegative. In... 相似文献
65.
A new sensor for simultaneous measurement of humidity and temperature is proposed. The sensor consists of Fabry–Perot cavity formed by two identical uniform fiber Bragg gratings. To make the cavity serves as humidity sensor, moisture sensitive polymer, which is polyimide, is coated on the FBG and on the cavity with different thickness. When the sensor is exposed to the relative humidity change, the polyimide will expand and stretch the fiber and induces strain on the FBG and on the cavity. The induced strain alters the grating period, cavity length and effective refractive index of fiber. The simulation results show that the humidity sensitivity and thermal sensitivity are 1.92 pm/%RH and 8.87 pm/°C, respectively, for polyimide coating thickness of 10 μm on the FBG and 15 μm on the cavity. 相似文献
66.
67.
Muhammad Anwar 《Tetrahedron letters》2007,48(41):7259-7262
Regioselective Dieckmann and aldol cyclisations using an N-acyloxazolidine derived from threonine give substituted tetramic acids and pyroglutamates in high yield and enantioselectivity. These are easily deprotected under mild conditions to give products, some of which exhibit antibacterial activity. 相似文献
68.
Steady two‐dimensional natural convection in an inclined parallel‐walled channel was investigated numerically. The full elliptic forms of conservation equations were solved together and the velocity vectors, temperature contours and local and average Nusselt number distribution were obtained. The comparisons of local and average Nusselt number with published experimental and numerical results indicate very good agreement. Results are presented for a single aspect ratio, L/b=24, over the range of Rayleigh number of 3–1000 and angle of inclination 0–90°. The results indicate that the overall channel average Nusselt number is reduced as the inclination angle is increased. Significant reductions in the overall Nusselt number are exhibited at high angle of channel inclination. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
69.
Dark transient capacitance measurements have been used to investigate the deeplevel content of red GaP LEDs. Thermal emission rate data is obtained and the 0.75 eV “killer” centre is identified from the signature. 相似文献
70.
Summary The magnetic susceptibilities of certain vanadium pentoxide systems supported by kieselgur have been determined in the temperature
interval 30° to 400° C. The plot of reciprocal susceptibility against temperature for all the systems studied indicates sudden
deflections at temperatures which are about 150° lower than those of optimum catalytic activity. It has been suggested that
these points may mark the temperatures of commencement of structural changes which may be responsible for the activity of
these catalysts.
Zusammenfassung Die magnetische Susceptibilit?t gewisser Vanadium-Pentoxyd-Systeme mit Kieselgur als Tr?ger wurden im Temperaturintervall zwischen 30 und 400° C bestimmt. Die Auftragung der reziproken Susceptibilit?t gegen die Temperatur zeigt für alle untersuchten Systeme pl?tzliche Knicke bei Temperaturen, die etwa 150° niedriger liegen als die optimale katalytische Aktivit?t. Es wird vermutet, da? diese Knickpunkte die Temperaturen des Beginns von Struktur?nderungen zeigen, die für die Aktivit?t dieser Katalysatoren verantwortlich sind.相似文献