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1.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献
2.
P. E. Cladis 《Journal of statistical physics》1991,62(5-6):899-925
We first discuss nonlinear aspects of phase transition theory applied to a particular liquid crystal phase transition. A simple derivation is given to show how two coupled Goldstone modes (one appearing as gauge fluctuations of the ordered phase) can force a phase transition, against all expectations, to take place discontinuously (theory of Halperin, Lubensky, and Ma)-but the discontinuity may be immeasurably small. Then, we describe a new dynamical test of phase transition order, developed by Cladiset al., that turns out to be more sensitive than x-ray diffraction and adiabatic calorimetry. Quantitative data found by this new method are in excellent agreement with the measurements of adiabatic calorimetry and x-ray diffraction as well as expectations implicit in the predictions of HLM.This is the text of an after-banquet talk given at the CNLS Workshop on the Dynamics of Concentrated Systems. 相似文献
3.
The spin-1 Ising model, which is equivalent to the three-component lattice gas model, is used to study wetting transitions in three-component surfactant systems consisting of an oil, water, and a nonionic surfactant. Phase equilibria, interfacial profiles, and interfacial tensions for three-phase equilibrium are determined in mean field approximation, for a wide range of temperature and interaction parameters. Surfactant interaction parameters are found to strongly influence interfacial tensions, reducing them in some cases to ultralow values. Interfacial tensions are used to determine whether the middle phase, rich in surfactant, wets or does not wet the interface between the oil-rich and water-rich phases. By varying temperature and interaction parameters, a wetting transition is located and found to be of the first order. Comparison is made with recent experimental results on wetting transitions in ternary surfactant systems.This paper is dedicated to J. K. Percus in honor of his 65th birthday. 相似文献
4.
A convective flow CO laser composed of polytetrafluoroethylene discharge tubes, nickel–chromium steel components, a cupric heat exchanger and other components is described. Operating in liquid nitrogen condition, output power of 60 W has been obtained from a non-selective cavity. 相似文献
5.
Basic principles of the generalized lattice model of multicomponent condensed systems are formulated. Short-range parts of interatomic interactions are taken into account by means of the geometric constraints method. Long-range parts of the interactions are taken into account in mean field approximation. The expression for Helmholtz free energy is obtained. A system of integral equations for the equilibrium distributions of components is derived. The asymptotic properties of its solutions are investigated. Moment expansion of interatomic interactions and localization of integral terms in free energy is obtained. A Ginzburg–Landau-like functional of free energy is derived. 相似文献
6.
建立了相变热力学理论和场论的关系. 强调在量子场论中必须引进序参量场, 则相变的讨论就类似于Goldstone bosons 的产生. 如果只讨论一级相变, Goldstone bosons场就足够了; 如果要讨论二级相变, 则必须讨论一系列的场, 这些场构成一个对称群的表示. 另外, 也将这一思想用到色超导中. In this paper we built a relation between the thermodynamical theory of the phase transition and field theory. We emphasized that in the quantum field theory we have to introduce the order parameter fields. Then the discussion of the phase transition is closed to the creation of the Goldstone bosons. If we only discuss the first order transition, the Goldstone bosons fields are sufficient. If we want to discuss the second order transition, we have to discuss a set of fields that constructs a representation of a symmetry group. We also apply this concept to color superconductivity. 相似文献
7.
H.L. Xu A. Persson S. Svanberg 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2003,23(2):233-236
New radiative lifetime measurements based on time-resolved laser-induced fluorescence techniques are reported for 18 even-parity
levels belonging to the 4f5d26p and 4f
25d
2 configurations of Ce I and 6 even-parity levels belonging to the 5d26s, 4f5d6p, and 4f6s6p configurations of Ce II. Free neutral and singly ionized cerium atoms were produced by laser ablation. The Ce I and Ce II
levels range in energy from 26 545 to 29 102 cm-1, and 42 573 to 48 152 cm-1, respectively.
Received 25 September 2002 Published online 4 March 2003 相似文献
8.
Hiroto Kudo Nobuhito Ito Keiji Nakajima Masami Ochiai Tadatomi Nishikubo 《Journal of polymer science. Part A, Polymer chemistry》2007,45(19):4421-4429
The polyaddition of fluorine‐containing bis(epoxide)s and fluorine‐containing triazine di(aryl ether)s were examined to give the corresponding fluorine‐containing poly(cyanurate)s. It was observed that the synthesized fluoropolymers had good thermal stabilities and good film‐forming properties. The glass transition temperatures (Tg's) and refractive‐indices (nD's) of synthesized polymers were determined by differential scanning calorimetry and ellipsometry, respectively, and it was found that the values of Tg's and nD's were supported by their fluorine containing ratios and skeletons. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4421–4429, 2007 相似文献
9.
Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) (M‐PAEK) and poly(aryl ether ether ketone) (PEEK) has been investigated by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM) techniques. The measurements reveal that the formation of the rhythmically grown ring‐banded spherulites in the M‐PAEK/PEEK blends is strongly dependent on the blend composition. In the M‐PAEK‐rich blends, upon cooling, an unusual ring‐banded spherulite is formed, which is ascribed to structural discontinuity caused by a rhythmic radial growth. For the 50:50 M‐PAEK/PEEK blend, ring‐banded spherulites and individual PEEK spherulites coexist in the system. In the blends with PEEK as the predominant component, M‐PAEK is rejected into the boundary of PEEK spherulites. The cooling rate and crystallization temperature have great effect on the phase behavior, especially the ring‐banded spherulite formation in the blends. In addition, the effects of M‐PAEK phase transition rate and phase separation rate on banded spherulite formation is discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3011–3024, 2007 相似文献
10.
You‐Liang Zhao Chuan‐Fu Chen Fu Xi 《Journal of polymer science. Part A, Polymer chemistry》2003,41(14):2156-2165
The atom transfer radical copolymerization of N‐substituted maleimides such as N‐phenylmaleimide (PhMI), N‐cyclohexylmaleimide (ChMI), and N‐butylmaleimide (NBMI) with styrene initiated with dendritic polyarylether 2‐bromoisobutyrates in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF6]), at room temperature and anisole at 110 °C was investigated. The dendritic‐linear block copolymers obtained in ionic liquid possessed well‐defined molecular weight and low polydispersity (1.05 < Mw/Mn < 1.32) and could be used as a macroinitiator for chain‐extension polymerization, suggesting the living nature of the reaction system. The ionic liquids containing catalyst could be recycled in the atom transfer radical polymerization systems without further treatment. Compared with polymerization conducted in anisole, the polymerization in ionic liquid had a stronger tendency for alternation. The tendency for alternation decreased in the order PhMI > NBMI > ChMI in [bmim][PF6] and PhMI > ChMI > NBMI in anisole. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2156–2165, 2003 相似文献