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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.
Masaaki Sugihara 《Numerische Mathematik》1997,75(3):379-395
Summary. In the light of the functional analysis theory we establish the optimality of the double exponential formula. The argument
consists of the following three ingredients: (1) introduction of a number of spaces of functions analytic in a strip region
about the real axis, each space being characterized by the decay rate of their elements (functions) in the neighborhood of
the infinity; (2) proof of the (near-) optimality of the trapezoidal formula in each space introduced in (1) by showing the
(near-) equality between an upper estimate for the error norm of the trapezoidal formula and a lower estimate for the minimum
error norm of quadratures; (3) nonexistence theorem for the spaces, the characterizing decay rate of which is more rapid than
the double exponential.
Received September 15, 1995 / Accepted December 14, 1995 相似文献
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In this paper, we provide numerical means to compute the quasi-stationary (QS) distributions inM/GI/1/K queues with state-dependent arrivals andGI/M/1/K queues with state-dependent services. These queues are described as finite quasi-birth-death processes by approximating the general distributions in terms of phase-type distributions. Then, we reduce the problem of obtaining the QS distribution to determining the Perron-Frobenius eigenvalue of some Hessenberg matrix. Based on these arguments, we develop a numerical algorithm to compute the QS distributions. The doubly-limiting conditional distribution is also obtained by following this approach. Since the results obtained are free of phase-type representations, they are applicable for general distributions. Finally, numerical examples are given to demonstrate the power of our method. 相似文献
6.
Recently extremal double circulant self-dual codes have been classified for lengths n ≤ 62. In this paper, a complete classification
of extremal double circulant self-dual codes of lengths 64 to 72 is presented. Almost all of the extremal double circulant
singly-even codes given have weight enumerators for which extremal codes were not previously known to exist. 相似文献
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8.
The potential of the internal rotation of the methyl group was determined for o-, m-, and p-fluorotoluene cations by pulsed field ionization spectroscopy. The potential of the internal rotational motion was also surveyed for other toluene derivative cations. It was found that the barrier height generally increases by ionization. The increase in the barrier height has been discussed in connection with the reduction of the internal rotational constant B by ionization. The geometrical distortion of the methyl group during the internal rotation has been suggested. 相似文献
9.
Shigeru Tasaka Norihiro Inagaki Masaaki Igawa 《Journal of Polymer Science.Polymer Physics》1991,29(6):691-694
The permeability of annealed poly (l-(trimethylsilyl)-l-propyne) was studied from the viewpoint of structural information obtained from x-ray diffraction and density. The sample cast from benzene solution had low density (0.82 g/cm3) and high permeability, whereas the annealed sample had a higher density (0.88 g/cm3) and permeability lower by two orders of magnitude. The smaller-angle x-ray diffraction peak for each sample, which was likely to reflect the distance between intermolecular chains, increased in intensity and shifted toward higher angle, corresponding to the change of the density with annealing. The logarithmic oxygen permeability was proportional to the density, namely the free volume fraction correlated with the diffusion coefficient and controlled by annealing and swelling by alcohols. 相似文献
10.
Suchada Suntornchashwej Dr. Khanit Suwanborirux Dr. Kazushi Koga Minoru Isobe Prof. Dr. 《化学:亚洲杂志》2007,2(1):114-122
Malyngamide X ( 1 ), the first (7R)‐lyngbic acid connected to a new tripeptide backbone, was isolated from the Thai sea hare Bursatella leachii. The gross structure of 1 was established on the basis of 1D and 2D NMR and mass spectroscopic data. Combination of the NMR spectroscopic experiments with α‐methoxy‐α‐(trifluoromethyl)phenylacetic acid esters, 2,2,2‐trifluoro‐1‐(9‐anthryl)ethanol chiral solvating agent, and molecular mechanics of 1 and the synthetic molecular fragments allowed us to determine the absolute stereochemistry of all six stereogenic centers without hydrolytic degradation of the compound. Compound 1 displayed moderate cytotoxic, antitubercular, and antimalarial properties. 相似文献