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991.
The decomposition of 1,1‐dimethyl‐1‐silacyclobutane (DMSCB) on a heated tungsten filament has been studied using vacuum ultraviolet laser single photon ionization time‐of‐flight mass spectrometry. It is found that the decomposition of DMSCB on the W filament to form ethene and 1,1‐dimethylsilene is a catalytic process. In addition, two other decomposition channels exist to produce methyl radicals via the Si? CH3 bond cleavage and to form propene (or cyclopropane)/dimethylsilylene. It has been demonstrated that both the formation of ethene and that of propene are stepwise processes initiated by the cleavage of a ring C? C bond and a ring Si? C bond, respectively, to form diradical intermediates, followed by the breaking of the remaining central bonds in the diradicals. The formation of ethene via an initial cleavage of a ring C? C bond is dominant over that of propene via an initial cleavage of a ring Si? C bond. When the collision‐free condition is voided, secondary reactions in the gas‐phase produce various methyl‐substituted 1,3‐disilacyclobutane molecules. The dominant of all is found to be 1,1,3,3‐tetramethyl‐1,3‐disilacyclobutane originated from the dimerization of 1,1‐dimethylsilene. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
992.
Shu‐Hui Yin Yufang Liu Wei Zhang Ming‐Xing Guo Peng Song 《Journal of computational chemistry》2010,31(10):2056-2062
In this work, the time‐dependent density functional theory (TDDFT) method was carried out to investigate the hydrogen‐bonded intramolecular charge‐transfer excited state of 2‐(4′‐N,N‐dimethylaminophenyl)imidazo[4,5‐b]pyridine (DMAPIP) in methanol (MeOH) solvent. All the geometric conformations of the ground state and locally excited (LE) state and the twisted intramolecular charge‐transfer (TICT) state for isolated DMAPIP and its hydrogen‐bonded complexes have been optimized. At the same time, the absorption and fluorescence spectra of DMAPIP and the hydrogen‐bonded complexes in different electronic states are also calculated. We theoretically demonstrated for the first time that the intermolecular hydrogen bond formed between DMAPIP and MeOH can induce the formation of the TICT state for DMAPIP in MeOH solvent. Therefore, the two components at 414 and 506 nm observed in the fluorescence spectra of DMAPIP in MeOH solvent were reassigned in this work. The fluorescence peak at 414 nm is confirmed to be the LE state. Furthermore, the red‐shifted shoulder at 506 nm should be originated from the hydrogen‐bonded TICT excited state. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
993.
Michal Horá?ek Ivana Císa?ová Ji?í Pinkas 《Journal of organometallic chemistry》2010,695(21):2338-1045
The singly tucked-in titanocene [Ti(η5-C5Me5)(η5:η1-C5Me4CH2)] (1) reacts smoothly with ethylene glycol or hydroquinone to give bis(titanoceneoxide) (TiIII) complexes [CH2OTi(η5-C5Me5)2]2 (2) and [(η5-C5Me5)2TiOC6H4OTi(η5-C5Me5)2] (3) containing dimethylene and 1,4-phenylene link, respectively. EPR spectra of 2 in 2-methyltetrahydrofuran glass and 3 in toluene glass revealed that the unpaired d1 electrons are in interaction to form triplet state molecules. The Ti-Ti distance derived from the zero-field splittings D for the two conformations of 2 (7.42 Å and 7.66 Å) are in good agreement with the Ti-Ti distance of 7.2430(7) Å from the X-ray diffraction single-crystal analysis. For 3, however, the Ti-Ti distance derived from D (7.65 Å) is by 1.47 Å shorter than the crystallographic distance of 9.1230(8) Å that indicates an enhancement of the through-space dipole-dipole interaction due to the presence of a conjugated quinonide link. 相似文献
994.
The mechanistic details of the pressure-induced B1-B2 phase transition of rubidium chloride are investigated in a series of transition path sampling molecular dynamics simulations. The B2→B1 transformation proceeds by nucleation and growth involving several, initially separated, nucleation centers. We show how independent and partially correlated nucleation events can function within a global mechanism and explore the evolution of phase domains during the transition. From this, the mechanisms of grain boundary formation are elaborated. The atomic structure of the domain-domain interfaces fully support the concept of Bernal polyhedra. Indeed, the manifold of different grain morphologies obtained from our simulations may be rationalized on the basis of essentially only two different kinds of Bernal polyhedra. The latter also play a crucial role for the B1→B2 transformation and specific grain boundary motifs are identified as preferred nucleation centers for this transition. 相似文献
995.
Paul J. Saines Dr. Brent C. Melot Ram Seshadri Prof. Anthony K. Cheetham Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(25):7579-7585
An anhydrous manganese succinate, Mn(C4H4O4), has been synthesised hydrothermally and studied by single‐crystal X‐ray diffraction. It adopts a succinate pillared structure in which layers of corner‐sharing MnO6 octahedra alternate with sheets that contain chains of edge‐sharing octahedra. This unique 3D framework structure contains highly distorted MnO6 octahedra, which are made possible by the lack of ligand field stabilisation energy for the high‐spin Mn2+ ion. Attempts to dope the structure with other divalent transition‐metal ions were accordingly unsuccessful. Magnetic susceptibility and heat capacity measurements indicate that Mn(C4H4O4) undergoes antiferromagnetic ordering below 12 K, with a second antiferromagnetic transition at approximately 6 K. These two antiferromagnetic phases undergo further transitions in applied fields, underlining the subtle magnetic behaviour that is possible in inorganic–organic frameworks of this structural complexity. 相似文献
996.
Abstract Evaluation of potential economic consequences of alternative management actions requires an understanding of how the biological stock will be affected by the management action and an understanding of the response of economic systems to changes in the timing, magnitude, and size distribution of harvests and changes in the location and catchability of the biological stock. We use a hybrid structural time series model to represent Pacific halibut (Hippoglossus stenolepis) stock and recruitment dynamics and a system of structural equations to represent supply and demand relationships for Pacific halibut from Alaska and British Columbia. Model simulations explore the economic effects of changes in recruitment success, growth rate, and carrying capacity, and changes in international supplies of halibut. 相似文献
997.
998.
使用 Langmuir-Hinshelwood (L-H) 动力学的学者大部分未注意到该动力学包含了所有吸附物种采用拟稳态假设的隐含条件, 因而他们通常忽视了确认实验条件是否允许采用拟稳态假设. 然而, 对于大部分气固催化反应, 拟稳态假设的成立需基于催化活性位浓度很小的前提. 对于催化活性位浓度高的反应体系, 其覆盖度较高的吸附物种不满足拟稳态假设. 因此, 在这种情况下通过实验测定的动力学常数没有物理意义, 而仅为该实验条件下的数学回归参数. 本文将活性位浓度小于最高反应气浓度的十分之一视为拟稳态假设成立的充分条件, 通过估算发现许多催化剂并不满足该条件. 相似文献
999.
The Yb3+-doped LiGd(MoO4)2 crystal with the size up to Φ20×30 mm3 has been grown by Czochralski technique.The polarized room temperature absorption and emission spectra have been investigated.This crystal exhibits a broad absorption band centered at 975 nm with an FWHM of 43 and 59 nm for π-and σ-polarization,respectively,and the corresponding maximal absorption cross-sections are 3.36 and 2.42×10-20 cm2.The emission broadband has an FWHM of 47 and 54 nm for π-and σ-polarization,respectively,with the corresponding emission cross sections of 3.92 and 3.34 × 10-20 cm2 at 1020 nm.The measured fluorescence lifetime is 287 μs. 相似文献
1000.
Nanocrystals of Ce1-xMnxO2-δ(x=0.00,0.05,0.10,0.15,and 0.20) were synthesized by a hydrothermal reaction route.The solid solutions crystallized in a cubic fluorite structure with a particle size in the range of 11~15 nm.The incorporation of Mn ions in CeO2 resulted in a lattice volume reduction.Mn ions showed a mixed valence state of +2,+3 and +4 in CeO2 lattice.An obvious red-shift of the absorption threshold edge was observed from the UV-visible spectrum.Compared with the bulk CeO2,Ce1-xMnxO2-δ nanocrystals exhibited a lower releasing oxygen temperature as indicated by TPR technique. 相似文献