Calculation of vertical ionization potentials of difluoramine by perturbation corrections to koopmans' theorem

The vertical ionization potentials of difluoramine are calculated by perturbation corrections to Koopmans' theorem. The calculation shows that difluoraimine has three overlapping bands between 15 and 16 eV. The calculated results compare well with the experimental values. The photoelectron spectrum of difluoramine is compared with that of OF₂ and CH₂F₂.     

Reaction of η5-cyclopentadienylbis(triphenylphosphine)cobalt(I) with alkadiynes. Preparation and reactions of bicyclic cobalt metallocycles and a stable trimethylsilyl-substituted mono-complexed alkadiyne. Comments on the mechanism of cobalt-catalyzed alkyne cooligomerization

Reactions of η⁵-cyclopentadienylbis(triphenylphosphine)cobalt(I) (5) with several 2,n-alkadiynes (2) were investigated. Each of these reactions leads initially to a material in which one of the acetylene functional groups is π-coordinated to cobalt; this complex then undergoes conversion to a metallocycle. In cases where the two acetylene functions are connected by three- and four-carbon bridges (2b, 2c), metallocycles formed by intramolecular reaction of two acetylene functions in the same molecule may be isolated. In cases where the acetylene functions are joined by larger or smaller bridges, the reactions are more complex, and both inter- and intramolecular metallocycles are formed. Reactions of 5 with 1,8-bis(trimethylsilyl)-1,7-octadiyne (16) gives an isolable crystalline mono-acetylene complex (17), this material is stable in the solid state but undergoes conversion to metallocycle (18) in benzene solution. The relationship of these results to the mechanism of the CpCo(CO)₂-catalyzed benzocycloalkene synthesis is discussed; it is suggested that intramolecular metallocycles are intermediates in reactions leading to benzocyclopentanes and -cyclohexenes, but intermolecular metallocycles are probably involved in reactions leading to benzocyclobutenes.     

Isocyanide addition to MN2(CO)5(Ph2PCH2PPh2)2 and the formation of a four-electron doubly-bridging isocyanide

The reactions of Fe(CO)₅, Fe(CO)₄P(C₆H₅)₃, M(CO)₆ (M  W, Mo, Cr), and (CH₃C₅H₄Mn(CO)₃ with KH and several boron and aluminium hydrides were investigated. Iron pentacarbonyl was converted quantitatively to K⁺Fe(CO)₄-(CHO) by hydride transfer from KBH(OCH₃)₃ allowing isolation of [P(C₆H₅)₃]₂-Nⁿ⁺Fe(CO)₄(CHO)^? in 50% yield. Lower yields were obtained with LiBH(C₂H₅)₃, and other hydride sources gave little or no formyl product. The stability of Fe(CO)₄(CHO)^? in THP was found to depend on the cation, decreasing in the order [P(C₆H₅)₃]₂N⁺ > K⁺ > Na⁺ > Li⁺. No formyl complexes were isolated and no spectroscopic evidence for formyl formation was observed in the reactions of the other transition metal carbonyls with several hydride sources. Fe(CO)₄-P(C₆H₅)₃ gave K₂Fe(CO)₄ when treated with KHB(OCH₃)₃. When treated with LiBH(C₂H₅)₃, W(CO)₆ gave a mixture of HW₂(CO)₁₀^?and (OC)₅W(COC₂H₅)^?; the latter was methylated to give the carbene complex (OC)₅WC(OCH₃)C₂H₅.     

Input,flux, and persistence of six select pesticides in San Francisco Bay

Temporal patterns of pesticide inputs to San Francisco Bay were identified and correlated with timing of application and transport mechanism. Fluxes were calculated from measured concentrations and estimated flow. Persistence of the pesticides under typical riverine or estuarine conditions were estimated from laboratory experiments. Simazine was detected most frequently and had the highest flux into the Bay, which could be explained by its continuous use and long half-life. In comparison, diazinon was detected at lower concentrations and had a lower flux which corresponded to its lower use and shorter half-life. The order-of-magnitude lower fluxes of carbofuran and methidathion corresponded to their lower use and expected hydrolysis. Molinate was detected at the highest concentration but its flux was lower than expected, considering its very high use and persistence in the laboratory experiments. Additional loss of molinate is likely to occur from volatilization and photodegradation on the rice fields. Although thiobencarb had the second highest use, it had the lowest flux of the six pesticides, which can be attributed to its loss via hydrolysis, photodegradation, volatilization, and sorption to sediments. Fluxes into San Francisco Bay were equal to or greater than those reported for other estuaries, except for the Gulf of Mexico.     

Vibrational lineshapes of adsorbates: the role of substrate electronic excitations

The vibrational spectrum of an atom or molecule adsorbed on a metallic surface is influenced by the dynamic interaction between the localized oscillator and the continuum of electron-hole pair excitations in the solid. Features of an exactly soluble model for this interacting system are presented, the local spectral function is obtained in terms of calculable level shift and broadening functions, and some prototypical numerical results are displayed and discussed.     

Conduction electron spin resonance in acceptor-type graphite intercalation compounds

An initial survey of the conduction electron spin resonance is presented for a series of graphite compounds intercalated with acceptor molecules: stages 1–3 AsF₅, stages 2–5 HNO₃, and stage 2 Br₂ and ICl. The g-values and lineshapes were studied as functions of temperature and concentration. The results suggest metallic behavior but with very small density of states at the Fermi energy: N(E_F) ～10²⁰/cm³ eV. The temperature dependence of the linewidth is dominated by an order-disorder transition of the intercalant layers, implying that the conduction electrons are not entirely confined to the graphite portion of the crystal. The decrease in g-value anisotropy upon intercalation can be understood in terms of Elliott's theory.     

皖中膨胀土的承载比(CBR)强度特性研究

针对皖中地区高速公路建设中遇到的膨胀土问题,选取合六叶高速公路典型土样开展了系统的承载比（CBR）特性试验研究,并在此基础上探讨了膨胀土作为路基填料的适用性。研究表明:（1）起始含水量对膨胀土CBR值影响显著,CBR最大值对应的含水量高于最佳含水量,且击实功越大,二者差值也越大;（2）CBR膨胀量随起始含水量增大而减小,起始含水量越低,CBR膨胀量就越大,路基的水稳性就越差;（3）当击实功较大时,膨胀土的最佳含水量较小,适合填筑的可变含水量范围较宽,建议现场施工控制采用重型击实标准;（4）在重型击实条件下,将弱膨胀土起始含水量控制在比最优含水量大2%⁴%范围内,能同时满足压实度和CBR值要求以用于填筑下路堤,中膨胀土作为路基填料时必须经过改性处理。研究结果对于在膨胀土地区进行公路建设具有参考意义。     

Influence of surface relaxation on the IR spectrum of microcrystalline MgO

Relaxation effects on the infrared spectra of microcrystalline MgO prepared under controlled conditions have been studied both by varying the average particle size and by chemisorption of pyndine. The results are compared with the phonon density of states distribution calculated by other authors.     

Intrinsic surface binding energy shifts in Yb metal

We report on the four-peak structure observed in the region of 4f photoemission in Yb metal, using synchrotron radiation in the energy range 70–200 eV. We conclude, contrary to previous reports, that the doublet associated with surface emissions results from an intrinsic surface shift on clean regions of the surface. We also demonstrate that the observed structure is consistent with earlier XPS measurements, and we set an upper limit on the width of the bulk peaks.