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71.
Katsufumi Hashimoto 《International journal of quantum chemistry》1985,28(5):581-591
Some accurate results on the length dependence of the excitation energies from the ground state to ionic excited states in the Hubbard model of linear polyenes are obtained based on the method of Lieb and Wu. To this end, it is first shown that singly ionic excited states with “plus” alternancy symmetry in the Hubbard model are described by the wave functions in which the two electron operator [∑(?)nCC] is acted on (N ? 2)-electron covalent eigenstates. Then by solving the Lieb-Wu equations the exact excitation energies of the lowest ionic state, which corresponds to the E state in this model, are calculated for systems with up to 50 electrons. The result, together with a correction for the end effect, indicates that the excitation energies do not decrease as 1/N but converge to the limiting value more rapidly when the number of electrons N becomes large. 相似文献
72.
The electronic and spin states of a series of Co-Fe Prussian blue analogues containing Na(+) ion in the lattice, Na(x)()Co(y)()Fe(CN)(6) x zH(2)O, strongly depended on the atomic composition ratio of Co to Fe (Co/Fe) and temperature. Compounds of Co/Fe = 1.5 and 1.15 consisted mostly of the Fe(III)(t(2g)(5)e(g)(0), LS, S = 1/2)-CN-Co(II)(t(2g)(5)e(g)(2), HS, S = 3/2) site and the Fe(II)(t(2g)(6)e(g)(0), LS, S = 0)-CN-Co(III)(t(2g)(6)e(g)(0), LS, S = 0) site, respectively, over the entire temperature region from 5 to 350 K. Conversely, compounds of Co/Fe = 1.37, 1.32, and 1.26 showed a change in their electronic and spin states depending on the temperature. These compounds consisted mainly of the Fe(III)-CN-Co(II) site (HT phase) around room temperature but turned to the state consisting mainly of the Fe(II)-CN-Co(III) site (LT phase) at low temperatures. This charge-transfer-induced spin transition (CTIST) phenomenon occurred reversibly with a large thermal hysteresis of about 40 K. The CTIST temperature (T(1/2) = (T(1/2) descending + T(1/2) ascending)/2) increased from 200 to 280 K with decreasing Co/Fe from 1.37 to 1.26. Furthermore, by light illumination at 5 K, the LT phase of compounds of Co/Fe = 1.37, 1.32, and 1.26 was converted to the HT phase, and the relaxation temperature from this photoproduced HT phase also strongly depended on the Co/Fe ratio; 145 K for Co/Fe = 1.37, 125 K for Co/Fe = 1.32, and 110 K for Co/Fe = 1.26. All these phenomena are explained by a simple model using potential energy curves of the LT and HT phases. The energy difference of two phases is determined by the ligand field strength around Co(II) ions, which can be controlled by Co/Fe. 相似文献
73.
Hashimoto T. Yoshinaga M. Ueda Y. Komazaki K. Asaoka K. Wang S. 《Journal of Thermal Analysis and Calorimetry》2002,69(3):909-917
The phase transitions of Ba2-xSrxIn2O5 were investigated with various thermal analyses and high-temperature X-ray diffraction. It was clarified that crystal structure
of Ba2-xSrxIn2O5 with x=0.0~0.4 varies from brownmillerite through distorted perovskite to another distorted perovskite with increase of temperature.
The phase transition from brownmillerite to distorted perovskite was revealed to be first order, whereas transition from distorted
perovskite to another one was second order. The specimen with x≥0.5 showed only one first order phase transition from brownmillerite to distorted perovskite. The phase diagram of Ba2-xSrxIn2O5 was established and existence of tricritical point at ~1100°C with x=0.4~0.5 was suggested.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
74.
[reaction: see text] Copper-mediated homocoupling of sterically hindered 2-(2,4,6-tri-tert-butylphenyl)-1-trialkylsilyl-2-phosphaethenyllithiums afforded 1,2-bis(trialkylsilyl)-3,4-diphosphacyclobutenes (1,2-dihydrodiphosphetenes) through a formal electrocyclic [2+2] cyclization in the P=C-C=P skeleton as well as 2-trimethylsilyl-1,4-diphosphabuta-1,3-diene. Reduction of 1,2-bis(trimethylsilyl)-3,4-diphosphacyclobutenes followed by quenching with electrophiles afforded ring-opened products, (E)-1,2-bis(phosphino)-1,2-bis(trimethylsilyl)ethene and (Z)-2,3-bis(trimethylsilyl)-1,4-diphosphabut-1-ene. The structures of the ring-opened products indicated E/Z isomerization around the C=C bond after P-P bond cleavage of 5, and the isomerization of the P-C=C skeleton. Ring opening of 1,2-bis(trimethylsilyl)-3,4-diphosphacyclobutenes affording (E,E)- and (Z,Z)-1,4-diphosphabuta-1,3-dienes was observed upon desilylation. 相似文献
75.
K. Hashimoto S. Hirota Y. Kanari Y. Hirai 《Journal of Radioanalytical and Nuclear Chemistry》2002,252(2):287-291
More than 200 samples of marine products have been collected and analyzed for plutonium and almost 100 samples for americium around Hitachi, Tokai and Oarai in the pacific coast of Ibaraki prefecture. The data have shown that the concentration factor (CF) values for plutonium were 330 for bivalve, 770 for abalone (muscle) and 610 for brown algae. For americium, the CF was calculated as 2400 for bivalve, 1000 for abalone (muscle) and 420 for brown algae. 相似文献
76.
Ptilomycalin A and crambescidins, novel marine guanidine alkaloids, have a unique pentacyclic guanidine structure, and exhibit a considerable array of biological activities. The first method developed for the synthesis of the pentacyclic guanidine core structure involved successive 1,3-dipolar cycloaddition reactions and resulted in the first total synthesis of crambescidin 359. The synthesis of other pentacyclic guanidine derivatives has been based on this methodology and applied as tools for studying biological activities, and as chemical reaction catalysts. 相似文献
77.
T. Hashimoto Y. Uezu F. Ishizuka H. Washio 《Journal of Radioanalytical and Nuclear Chemistry》1993,173(1):87-97
A selective extraction of the correlated events due to three kinds of short-lived -decay events,216Po (145 ms),217At (32.3 ms) and215Po (1.78 ms), from other random background events were examined by using a time interval analysis (TIA) from the viewpoint of detection sensitivity. In the theoretical treatment based on the probability and statistics, it was clarified that the detection sensitivity proportionally increased with shortening half-lives in the following order,215Po>217At>216Po. In the experiments, pulses from a liquid scintillator owing to -decay events were analyzed using a multiple TIA technique and resulted in the highest sensitivity of219Rn–215Po pairs in the actinium series. Thus, the multiple TIA method was applied to the practical determination of219Rn–215Po pairs in natural samples. 相似文献
78.
[formula: see text] The conformation of the retinal chromophore in rhodopsin is central for understanding the visual transduction process. The absolute twist around the 12-s bond of the chromophore in rhodopsin has been determined by studies with 11-cis-locked 11,12-cyclopropylretinal analogues (11S,12R)-2 and (11R,12S)-3, enantioselectively synthesized with the aid of an enzyme. The finding that enantiomer 2 binds to opsin while the other 3 does not defines the absolute sense of twist around the 12-s bond. 相似文献
79.
Yamamura K Houda Y Hashimoto M Kimura T Kamezawa M Otani T 《Organic & biomolecular chemistry》2004,2(9):1413-1418
Intramolecular reaction of 2-tropylio-3-(5-substituted 2-furyl)benzothiophenes (3), prepared from the corresponding 2-cycloheptatrienyl-3-(5-substituted 2-furyl)benzothiophenes (2), afforded the beta-(azuleno[1,2-b]benzothienyl)-alpha,beta-unsaturated ketones (4), which are otherwise difficult to obtain, in moderate yields. The reaction involves a ring-opening process of the furan ring by intramolecular attack of the tropylium ion onto the 2-position of the furan ring. Similarly, beta-(azuleno[2,1-b]benzothienyl)-alpha,beta-unsaturated ketones (8) were obtained from the corresponding 3-tropylio-2-(5-substituted 2-furyl)benzothiophenes (7) albeit in lower yields. The molecular and crystal structures of the methyl ketone derivative, 8a, are discussed on the basis of X-ray structure analysis. 相似文献
80.
Two novel nucleosides, mycalisines A and B, have been isolated from a marine sponge and their structures elucidated as 4-amino-5-cyano-7-(3--methyl-5-deoxy-β-D--pent-4-enofuranosyl)-pyrrolo[2,3-]pyrimidine and 5-cyano-7-(3--methyl-5-deoxy-β-D--pent-4-enofuranosyl)-pyrrolo[2,3-]pyrimidine-4-one, respectively. Both compounds inhibit cell division of fertilized starfish eggs. 相似文献