A theoretical study of the ion pair SN2 reaction between lithium isocyanates with methyl fluoride with inversion and retention mechanism

This paper is devoted to a detailed theoretical study of an ion pair S_N2 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.     

Evidence of a Photo‐Radical Pathway Responsible of the Rearrangement of a Manganese(III)‐Schiff Base Complex in Solution

A new Mn^III‐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 Mn^III 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.     

Rotational analysis ofA 1Π-X 1Σ+ bands of P14N and P15N: Perturbatio studies in theA 1Π state

The ultraviolet band systemsA ¹Π-X ¹Σ⁺ of P¹⁴N and P¹⁵N were excited in an electrodeless tube containing traces of phosphorus specpure nitrogen and neon using a microwave discharge (2450 MHz). Bands of the isotopic species, P¹⁵N, were obtained using¹⁵N₂ enriched to 95.5%. Rotational analyses of eleven bands of P¹⁴N and sixteen bands of P¹⁵N were carried out. Three perturbing statese ³Σ⁻,d ³Δ andb ³Π, arising from the lower valence configurations were identified from the observed perturbations in thev′=0–4 levels of theA ¹Π state. Deperturbation studies led to the determination of molecular constants of the perturbing states. Vibrational assignments of the perturbing states were made from isotope shift studies.     

德摩根一致代数的度量化

我们给出了德摩根一致代数可伪度量化的一个充分必要条件。     

Ergodic isospectral theory of the Lax pairs of Euler equations with harmonic analysis flavor

Isospectral theory of the Lax pairs of both 3D and 2D Euler equations of inviscid fluids is developed. Eigenfunctions are represented through an ergodic integral. The Koopman group and mean ergodic theorem are utilized. Further harmonic analysis results on the ergodic integral are introduced. The ergodic integral is a limit of the oscillatory integral of the first kind.

     

Labile Interactions Defined in Crystalline Metal Complexes

The problems involved in identifying and quantifying labile interactions considered to influence complex compound structures are highlighted through the assessment of four different families of metal complexes for which extensive crystallographic data are available. Modification of the charge distribution within a ligand molecule as a result of coordination is one factor with a number of ramifications. A detailed analysis of evidence for both intra- and inter-molecular attractions in dimethylsulfoxide complexes of metal perchlorates is used to provide a basis for the consideration of weak interactions between complex ions involving forces including phenyl-group attractions, hydrogen bonding and cavity inclusion.     

Conjugacy relationship between M-convex and L-convex functions in continuous variables

By extracting combinatorial structures in well-solved nonlinear combinatorial optimization problems, Murota (1996,1998) introduced the concepts of M-convexity and L-convexity to functions defined over the integer lattice. Recently, Murota–Shioura (2000, 2001) extended these concepts to polyhedral convex functions and quadratic functions in continuous variables. In this paper, we consider a further extension to more general convex functions defined over the real space, and provide a proof for the conjugacy relationship between general M-convex and L-convex functions.Mathematics Subject Classification (1991): 90C10, 90C25, 90C27, 90C35This work is supported by Grant-in-Aid of the Ministry of Education, Culture, Sports, Science and Technology of Japan     

Saturated Commutative Spaces of Heisenberg Type

In this paper, we give a partial classification of commutative spaces of Heisenberg type. Several classification results were known previously. In order to avoid complicated technical details, we restrict ourselves to saturated commutative spaces. Our results are presented in Table II.     

n进制中非零数字之积函数的均值公式

设 N =a1nk1+ a2 nk2 +… + asnks( 1 aik2 >… >ks 0 ) ,a( N,n) =a1a2 … as,本文给出了均值 Ar( N ,n) =∑m相似文献   

利用V型三能级原子与相干态光场Raman相互作用传送未知原子态

描述了简并V型三能级原子与单模相干态光场的Raman相互作用,获得了处于激发态单态的原子与相干态光场相互作用的结果.利用探测原子与光场的相互作用将原子和光场制备成最大缠结态,并注入待测原子,通过原子与腔模构成的Bell基矢演化,对腔场进行选择性探测,获得探测原子相互作用后可能的量子状态,然后对待测原子与腔场进行联合探测,接着对探测原子的量子状态实施幺正变换,就将探测原子制备到待测原子的初始量子态上,从而实现未知原子态的隐形传送.