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1.
2.
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
3.
4.
A 1.5-μm eye-safe, 3-D scanning, and compact Mie LIght Detection and Ranging (LIDAR) is presented. The transmitter of the LIDAR is based on a KTA optical parameter oscillator (OPO) resonator. For detecting return signals, an InGaAs APD is used. The all solid-state OPO laser transmitter has the feature of small volume and lightweight, which allows a 165-lb compact eye-safe scanning LIDAR to be constructed. A system simulation using our own model was conducted to direct the system development. A method to solve the problem with small active area APD detectors was developed and described. The preliminary field-test measurement results indicated that the LIDAR has the capability to detect aerosols and clouds in lower atmospheres up to three dimensions. 相似文献
5.
The γcmc values of CTAB-SDS decrease from 63.67 mN/m at 10‡C to 36.38 mN/m at 90‡C, slightly lower than those of either CTAB or SDS.
Correspondingly, the CMC of CTAB-SDS decreases almost by half. The increase of surface activity of CTAB-SDS can be attributed
to the relatively weak electrostatic interaction at high temperature, which is supported by the increase of solubility of
CTAB-SDS with rise in temperature. Catalytic effect on oxidation of toluene derivatives with potassium permanganate follows
the order CTAB-SDS > SDS > CTAB. This is not caused by the dissociative effect of CTAB-SDS with low surface activity at low
temperature, as seen from the fact that almost all oxidative products can be retrieved for different toluene derivatives and
surfactants by mimicking the conditions of reaction. In the emulsifications of toluene derivatives at 90‡C, the time that
turbid water layers of surfactant solutions take to become clear is the same as that of the catalytic effect on oxidation
of toluene derivatives. Thus, it can be inferred that surfactants can improve the oxidation yields of toluene derivatives
by increasing the contact between two reacting phases. 相似文献
6.
Yu. V. Pokonova 《Russian Journal of Applied Chemistry》2007,80(12):2163-2164
Kinetic, sorption and selectivity properties of commercial adsorbents are improved by adding petroleum residues (tar asphaltene concentrates) 13% of whole mass. Obtained adsorbents can be used for selective extraction of nobel metals from multicomponent polymetallic solutions of heavy metals and fro sewages purification for removing arsenic. 相似文献
7.
8.
Experimental data on the effect of thallium and sodium impurities on the lattice heat conductivity of PbTe at room temperature
are reported. Because the lattice of lead chalcogenides is strongly polarized near charged impurities, the effect of impurities
on the lattice heat conductivity depends substantially on their charge state. This property of the material has been used
to determine the charge state of the thallium impurity in PbTe. The results obtained argue for a model of quasi-local thallium-impurity
states which assumes low electron-correlation energy at an impurity center.
Fiz. Tverd. Tela (St. Petersburg) 40, 1206–1208 (July 1998) 相似文献
9.
Yu. A. Sharin 《Russian Physics Journal》1998,41(5):447-450
Ideas previously enunciated by the author about the physical interpretation of curvilinear space with torsion are developed.
With the new equations describing the eigenstates of such a space, the static centrosymmetric solution for gravitational and
electric fields can be made consistent with the Newton and Coulomb laws. The asymptotic behavior of the axisymmetric solution
at infinity is studied. The gyromagnetic ratio obtained is characteristic of the electron.
Ural State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, p. 56–60, May, 1998. 相似文献
10.
C. Waldtmann H.-U. Everts B. Bernu C. Lhuillier P. Sindzingre P. Lecheminant L. Pierre 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,2(4):501-507
We study the exact low energy spectra of the spin 1/2 Heisenberg antiferromagnet on small samples of the kagomé lattice of up to N=36 sites. In agreement with the conclusions of previous authors, we find that these low energy spectra contradict the hypothesis
of Néel type long range order. Certainly, the ground state of this system is a spin liquid, but its properties are rather
unusual. The magnetic () excitations are separated from the ground state by a gap. However, this gap is filled with nonmagnetic () excitations. In the thermodynamic limit the spectrum of these nonmagnetic excitations will presumably develop into a gapless
continuum adjacent to the ground state. Surprisingly, the eigenstates of samples with an odd number of sites, i.e. samples with an unsaturated spin, exhibit symmetries which could support long range chiral order. We do not know if these
states will be true thermodynamic states or only metastable ones. In any case, the low energy properties of the spin 1/2 Heisenberg
antiferromagnet on the kagomé lattice clearly distinguish this system from either a short range RVB spin liquid or a standard chiral spin liquid. Presumably
they are facets of a generically new state of frustrated two-dimensional quantum antiferromagnets.
Received: 27 November 1997 / Accepted: 29 January 1998 相似文献