This paper is devoted to a detailed theoretical study of an ion pair SN2 reaction LiNCO+CH3F in the gas phase and in solution at the level of MP2(full)/6-31+G**//HF/6-31+G**. Two possible reaction mechanisms, inversion and retention, are discussed. There are eight possible reaction pathways. The inversion mechanism is more favorable no matter in the gas phase or in solution based on analyses of the transition structures. Methyl isocyanate should form preferentially in the gas phase and more stable methyl cyanate is the main product in solution. The retardation of the reaction in solvents was attributed to the difference in solvation in the separated reactants and in the transition state. 相似文献
The accuracy of determination of the optical constants of smooth copper surfaces produced by different technologies is analyzed, with particular attention paid to the consideration of the influence of scattered radiation (which is ignored by many authors) on the retrieval of the optical constants of copper surfaces from reflected radiation. The neglect of scattered radiation can lead to errors as high as 50% in determining the optical constants for bulk copper. For thin films, the errors are much lower. The influence of surface oxidation during measurements in air and surface features of studied objects on the parameters to be determined is analyzed as well. It is shown that errors in determination of the constants are maximal in the plasma resonance region of copper.
Comparing with the exact solutions of the model system of one and two particles coupled to an axial rotor, the quality of the semi classical tilted axis cranking approximation is investigated. Extensive comparisons of the energies and M1 and E2 transition probabilities are carried out for the lowest bands. Very good agreement is found, except near band crossings. Various recipes to take into account finite K within the frame of the usual principal axis cranking are included into the comparison. A set of rules is suggested that permits to construct the excited bands from the cranking configurations, avoiding spurious states. 相似文献
In the title compound, catena‐poly[lithium‐μ3‐ethylenediphosphonato], [Li(C2H7O6P2)]n, the supramolecular monoclinic (C2/c) structure consists of one‐dimensional lithium chains [Li⋯Li = 2.7036 (8) Å] that are embedded within ethylenediphosphonate anions linked by strong symmetric hydrogen bonds [O⋯O = 2.473 (3) Å]. The Li atoms and the H atom in the symmetric hydrogen bond reside on twofold rotation axes and there is an inversion center at the mid‐point of the C—C bond of the ethylenediphosphonate ligand. 相似文献
A new MnIII‐Schiff base complex, [MnL(OH2)](ClO4) ( 1 ) (H2L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode MnIII EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement. 相似文献