排序方式: 共有33条查询结果,搜索用时 83 毫秒
1.
Christopher Batich Edgar Heilbronner Martin F. Semmelhack 《Helvetica chimica acta》1973,56(6):2110-2112
For a given molecule M, the difference ΔI between the first two vertical ionization potentials Iv,2 and Iv,2 (from MOs ψ1 and ψ2) and ΔE between the corresponding singlet-singlet excitation energies E1 and E2 (transitions ψ?1 ←1, ψ?1 ψ2) are related by ΔE = ΔI- (J2,?1?J1,?1) ?2(K1,?1 ? K2,?1), using Koopmans approximation. A simple MO model suggests that under certain conditions of symmetry and quasi-alternancy (e. g. in spiro[4,4]nonatetraene 1 ) the bracketed differences between the Coulomb- and exchange-integrals should vanish to first order, thus leading to the simple (almost) equality ΔE = ΔI. It is shown that the results from a photoelectron- and electron-spectroscopic investigation of 1 support this conclusion i.e. ΔI = 1.23 eV, ΔE = 1.19 to 1.23 eV. 相似文献
2.
J. Horn H. -Ch. Semmelhack H. Börner F. Schlenkrich 《Journal of Thermal Analysis and Calorimetry》1994,41(5):995-1005
We propose a reaction model for the synthesis of YBa2Cu4O8 under normal pressure conditions, which contains 4 partial reaction steps. In a first step bariumnitrate and copperoxide react to Ba2Cu3O5+δ. This substance will be formed for each mixtures Ba:Cu=2∶3...3∶2. The following two partial reaction steps are connected to Ba2Cu3O5+δ, which reacts with Y2O3 and CuO to YBa2Cu4O8 or decomposes to BaCuO2 and CuO. In a last step parts of BaCuO2 reacts with Y2O3 and CuO to YBa2Cu4O8. 相似文献
3.
The decomposition of η6-(2-lithiochlorobenzene)tricarbonylchromium(0) (I) was found to follow first order kinetics with kdec 5.1 x 10-3 min-1 at 0°C, the half life of I being 136 min at 0°C. While this dependence strongly suggests intermediacy of η6-(benzyne)tricarbonylchromium, trapping experiments were successful in only low yield. 相似文献
4.
Andrea GotiMartin F. Semmelhack 《Journal of organometallic chemistry》1994,470(1-2):C4-C7
Arene displacement from the title complex occurs under unprecedented mild conditions in neutral media to afford (η6-arene)tricarbonylchromium complexes. The process is most effective with heteroaromatic compounds: the first synthesis of a tricarbonyl(η6-quinoline)chromium complex and the diastereoselective preparation of a (η6-indole) complex derived from L-tryptophan are reported as representative examples. 相似文献
5.
A series of novel organoiron complexes has been isolated and studied by 1H NMR, 13C NMR, and IR spectroscopy. Addition of LiC(CH3)2CN to (1,3-cyclohexadiene)tricarbonyliron produces an intermediate which is only stable at low temperature and which is assigned the homoallyl—Fe(CO)3 anion structure. The intermediate rearranges on warming into a stable complex, for which full spectral data support the structure as an allyl—Fe(CO)3 anionic species. Interception of the first formed intermediate with CO gives an acylferrate complex with an olefin unit still bound to iron, and methylation then occurs at oxygen to produce an unusual internally-bound (alkene)(methoxyalkylidene)tricarbonyliron species. 相似文献
6.
Experiments by Gittings, Bandyopadhyay and Durian (Europhys. Lett. 65, 414 (2004)) demonstrate that light possesses a higher probability to propagate in the liquid phase of a foam due to total
reflection. The authors term this observation photon channelling which we investigate in this article theoretically. We first
derive a central relation in the work of Gitting et al. without any free parameters. It links the photon's path-length fraction f in the liquid phase to the liquid fraction ɛ. We then construct two-dimensional Voronoi foams, replace the cell edges by
channels to represent the liquid films and simulate photon paths according to the laws of ray optics using transmission and
reflection coefficients from Fresnel's formulas. In an exact honeycomb foam, the photons show superdiffusive behavior. It
becomes diffusive as soon as disorder is introduced into the foams. The dependence of the diffusion constant on channel width
and refractive index is explained by a one-dimensional random-walk model. It contains a photon channelling state that is crucial
for the understanding of the numerical results. At the end, we shortly comment on the observation that photon channelling
only occurs in a finite range of ɛ. 相似文献
7.
8.
Simple benzopyrans with a fused γ-lactone unit are prepared from an o-disubstituted arene by direct intramolecular alkoxycarbonylation/lactonization promoted by palladium diacetate; the process gives high yields and moderate stereoselectivity, favoring the lactone over by a factor of 5:1. 相似文献
9.
10.