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51.
The third-rank electric hypershieldings at the nuclei of four small molecules have been evaluated at the Hartree-Fock level of theory in the Hellmann-Feynman approximation. The nuclear electric hypershieldings are closely related to molecular vibrational absorption intensities and a generalization of the atomic polar tensors (expanded in powers of the electric field strength) is proposed to rationalize these intensities. It is shown that the sum rules for rototranslational invariance and the constraints imposed by the virial theorem provide useful criteria for basis-set completeness and for near Hartree-Fock quality of nuclear shieldings and hypershieldings evaluated in the Hellmann-Feynman approximation. Twelve basis sets of different size and quality have been employed for the water molecule in an extended numerical test on the practicality of the proposed scheme. The best results are obtained with the R12 and R12+ basis sets, designed for the calculation of electronic energies by the explicitly correlated R12 method. The R12 basis set is subsequently used to investigate three other molecules, CO, N2, and NH3, verifying that the R12 basis consistently performs very well. 相似文献
52.
Linde C Koliaï N Norrby PO Akermark B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2568-2573
The substrate electronic effects on the selectivity in the catalytic epoxidation of para-substituted cis stilbenes 2a-i were investigated by using (R,R)-[N,N'-bis(3,5-di-tBu-salicylidene)-1,2-cyclohexanediamine]manganese(III) chloride 1 in benzene as the catalyst with iodosobenzene as the terminal oxidant. A Hammett study of the selectivity results reveals a stronger electrophilic character than previously assumed in the (salen)Mn-catalyzed reaction. In general, the best correlations with the experimental values were obtained by using the Hammett sigma + values, which gave rho = -1.37 for the rate of cis-epoxide formation and rho = -0.43 for the rate of the stepwise process leading to the corresponding trans product. The reaction involves two separate pathways as indicated also by the competitive breakdown of the intermediate on the path to trans epoxide for methoxy-substituted substrates. The asynchronicity in the concerted pathway leading to cis epoxide is apparent for 4-methoxy-4'-nitrostilbene, which yields cis epoxide with 75% ee entirely as a result of electronic effects. 相似文献
53.
Jörn Manz 《Chemical physics》1977,24(1):51-64
Energy stored in vibrational level ν = 1 of several individual dipolar diatomic molecules AB which are trapped in a rare gas matrix M is automatically accumulated in a higher level ν > 1 of a single molecule AB. This remarkable cascade of energy upwards competes with a cascade of energy downwards. the radiative decay. The interplay of both cascades, first observed by Dubost and Charneau, is explained a simple model. The model incorporates three processes into a master equation for the relative populations Pν(t) of levels ν: (a) migration of single quanta by resonance energy transfer, AB(1) + AB(0) ? AB(0) + AB(1); (b) phonon assisted excitation of upper levels, AB(1) + AB(ν) → AB(0) + AB(ν+1); and (c) radiative decay, AB(ν) → AB(ν-1). The model assumes that there is only one isotopic species AB which has a small but nonzero vibrational anharmonicity, that the temperature is low, T → 0 K, the concentration ratio ?M/?AB is large and that, initially, at time t = 0, a small fraction p1 of molecules AB is excited to level ν = 1. The master equation has only two parameters, the radiative lifetime trad and k 2/[?AB?1k(1,1 → 0,2)trad], where k(1,1 → 0,2) is the reference rate constant of process (b). The master equation is solved in closed form for the Pν(t). For trad = 14 ms and k = 0.2, very satisfactory qualitative agreement is found for the theoretical Pν(t) and the experimental time evolution of the relative population of vibrational levels of 12C16O in an argon matrix, for ?M/?AB = 2000 at T = 9 K. In agreement with experimental results it is concluded that the risetime of the fluorescence signals decreases whereas population inversion increases for decreasing values of ?M/?AB. At long times, t > trad, any population inversion should disappear. 相似文献
54.
Foltz C Stecker B Marconi G Bellemin-Laponnaz S Wadepohl H Gade LH 《Chemical communications (Cambridge, England)》2005,(40):5115-5117
Chiral C3-symmetric trisoxazolines are highly efficient stereodirecting ligands in enantioselective Cu(II) Lewis acid catalysis which is based on the concept of a stereoelectronic hemilability of the divalent copper; in direct comparison with the analogous bisoxazoline systems they are more efficient in the enantioselective alpha-amination as well as the enantioselective Mannich reaction of prochiral beta-ketoesters. 相似文献
55.
Earlier studies of electric field assisted LC (EF-LC) have shown that the effect on charged analytes of the application of an electric field over a capillary LC column is relatively small. Charged analytes can only be affected by the electric field while present in the mobile phase, which makes the effective time for influence of the electric field t(0) independent of retention time. Because the charged analytes only can be affected for a short time the electric field strength ought to be high in order to increase the impact of the electric field on the separation. We have, however, found that only a relatively low electric field strength can be used in EF-LC when pressure is used as main driving force. The useful field strength was limited by a dramatic increase in the current. This increase in current was found to origin from an increased concentration of buffer ions that have an electrophoretic mobility towards the pumped flow. 相似文献
56.
Annika Niklasson Ingemar Kvarnström Björn Classon Bertil Samuelsson 《Molecules Online》1998,2(1):7-14
Phosphonomethyl substituted 2?,3?-Dideoxy-3?-C-hydroxymethylcytidines have been synthesized and evaluated for their anti HIV-1 activities. The sugar moiety was synthesized starting from (S)-5-hydroxymethylfuran-2-(5H)-one using photocatalyzed addition of methanol. Reduction of the lactone, condensation with silylated 4-methoxy-2(1H)pyrimidinone, followed by phosphonomethylation and deprotection gave the title compounds. The compounds were tested for inhibition of HIV-1 activity but did not show any significant antiviral activity. 相似文献
57.
Enn?LustEmail author Alar?J?nes Tanel?P?rn Priit?Nigu 《Journal of Solid State Electrochemistry》2004,8(4):224-237
Electrochemical characteristics for the nanoporous carbon|Et4NBF4+acetonitrile interface have been studied by cyclic voltammetry and impedance spectroscopy methods. The influence of the electrolyte concentration and thickness of the nanoporous electrode material on the shape of the cyclic voltammetry and impedance curves has been established and the reasons for these phenomena are discussed. A value of zero charge potential, depending slightly on the structure and concentration of the electrolyte, the region of ideal polarizability and other characteristics have been established. The nanoporous nature of the carbon electrodes introduces a distribution of resistive and capacitive elements, giving rise to complicated electrochemical behaviour. Analysis of the complex plane plots shows that the nanoporous carbon|Et4NBF4+acetonitrile electrolyte interface can be simulated by an equivalent circuit, in which two parallel conduction paths in the solid and liquid phases are interconnected by the double-layer capacitance in parallel with the complex admittance of the hindered reaction of the charge transfer or of the partial charge transfer (i.e. adsorption stage limited) process. The values of the characteristic frequency depend on the electrolyte concentration and electrode potential, i.e. on the nature of the ions adsorbed at the surface of the nanoporous carbon electrode. The value of the solid state phase resistance established is independent of the thickness of the electrode material. 相似文献
58.
Summary Qualitative molecular orbital considerations of the complexes [5-CPV(CO)3 L] (L = substituted phosphane, SbPh3, AsPh3, CN–) suggest that s' V chemical shift parameters () obtained for these compounds should correlate with the -acceptor abilities of L. Based on observed r-values, the ligands are arranged in sequence of their -acceptor ability, which lies in the order P(OR)3 > CN– > PR'33 SbPh3 PPhF2 > P(i-Bu)3 P(NR
2
)3 > PPh3 > AsPh3 Nuclear spin-spin coupling constants J (51V-31 P), line widths H and i.r. data in the (CO) region are also presented.P(OR)3 = P(OEt)3, 4-Ethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]-octane; R = Me, n-Pr; R = Me, Et. 相似文献
59.
Using gas-phase electron diffraction it has been demonstrated that a composition of known isomer mixtures can be determined with error limits of about 5%, all relevant structural parameters being refined simultaneously by the least-squares method. If, however, corresponding bond distances and valence angles have erroneously been assigned equal values in the two isomers, a large increase in the least-squares error limits from 5% to 12% is noticed. Apparently innocent assumptions about some of the parameters can lead to incorrect isomer composition and to too small error limits as estimated by the least-squares formulae.
From the reinvestigation of pure cis-1,2-dichloroethene the following bond distances (ra) and valence angles () were determined: r(C---H) = 1.090(29) Å, r(C=C) = 1.345(6) Å, r(C---Cl) = 1.716(4) Å, C=C---Cl = 123.8(2)°, C=C---H = 119.4(26)°. Error limits are 2σ. 相似文献
60.
Xu Y Eilers G Borgström M Pan J Abrahamsson M Magnuson A Lomoth R Bergquist J Polívka T Sun L Sundström V Styring S Hammarström L Akermark B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(24):7305-7314
To mimic the electron-donor side of photosystem II (PSII), three trinuclear ruthenium complexes (2, 2a, 2b) were synthesized. In these complexes, a mixed-valent dinuclear Ru2(II,III) moiety with one phenoxy and two acetato bridges is covalently linked to a Ru(II) tris-bipyridine photosensitizer. The properties and photoinduced electron/energy transfer of these complexes were studied. The results show that the Ru2(II,III) moieties in the complexes readily undergo reversible one-electron reduction and one-electron oxidation to give the Ru2(II,III) and Ru2(III,III) states, respectively. This could allow for photooxidation of the sensitizer part with an external acceptor and subsequent electron transfer from the dinuclear ruthenium moiety to regenerate the sensitizer. However, all trinuclear ruthenium complexes have a very short excited-state lifetime, in the range of a few nanoseconds to less than 100 ps. Studies by femtosecond time-resolved techniques suggest that a mixture of intramolecular energy and electron transfer between the dinuclear ruthenium moiety and the excited [Ru(bpy)3]2+ photosensitizer is responsible for the short lifetimes. This problem is overcome by anchoring the complexes with ester- or carboxyl-substituted bipyridine ligands (2a, 2b) to nanocrystalline TiO2, and the desired electron transfer from the excited state of the [Ru(bpy)3]2+ moiety to the conduction band of TiO2 followed by intramolecular electron transfer from the dinuclear Ru2(II,III) moiety to photogenerated Ru(III) was observed. The resulting long-lived Ru2(III,III) state decays on the millisecond timescale. 相似文献