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991.
The doublet electronic states of ketene, and ketene-d2, radical cations produced by photoionisation with Helα (58.4 nm) and Hellα (30.4 nm) radiation, were studied by photoelectron spectroscopy. Seven such states were found below 28 eV ionisation energy and were assigned by comparison with the ionisation energies calculated by the correlated PNO-CEPA approach. The agreement is within ≈ 0.3 eV of the experimental data. An analysis of the contributions of reorganisation and correlation effects to the calculated ionisation energies is presented. The vibrational frequencies exciteα in four of the states of ketene-d2 and ketene are presented and discussed in view of the assignments. 相似文献
992.
993.
The kinetics of oxidative gas-phase dehydrogenation of isobutyraldehyde over Cs2HPMo12O40 catalyst has been studied in a flow-through integral reactor at 523 K at atmospheric pressure. The catalytic reaction has
been found to be accompanied by oxidation of isobutyraldehyde outside the catalyst bed. The rate of formation of methacrolein
is satisfactorily described by the rate equation derived on presumption of change in the mean activation energy. The rate
of the reaction in the homogeneous phase was described by empirical pseudo-first order equation.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
994.
995.
Kadlec F Kadlec C Kuzel P Slavícek P Jungwirth P 《The Journal of chemical physics》2004,120(2):912-917
The optical pump-terahertz probe spectroscopy was used together with ab initio calculations and molecular dynamics simulations to investigate ultrafast dynamics following electronic excitation of Coumarin 153 and TBNC (2,11,20,29-tetra-tert-butyl-2,3-naphtalocyanine) dyes in polar solvents. By scanning the terahertz waveform for different pump-probe delays this experimental technique allows us to obtain two dimensional spectra directly reflecting the temporal response of the system. A distinct signal was obtained for TBNC in chloroform, 2-propanol, and n-butanol, while no signal was recorded for Coumarin 153 in either of these solvents. We explain the nonequilibrium signal detected in TBNC solutions by the presence of a solid, polycrystalline phase of the dye resulting from irradiating the solution by intense optical pulses. 相似文献
996.
Analytical characterization of monoclonal antibodies has been hindered by the lack of appropriate chromatographic methods to be used in conjunction with high-resolution MS. Current methodologies for standard RP-HPLC are incompatible with antibodies due to irreproducibility, low recovery, short column lifetimes, and poor resolution of degradation products. An analytical RP-HPLC-MS method was developed for monitoring and characterizing intact IgG1antibodies. Key parameters required for improved chromatographic resolution included long alkyl chains of the stationary phase (Zorbax SB300 C8), column temperatures elevated to 65-70 degrees C and combination of trifluoroacetic acid and heptafluorobutyric acid ion-pairing agents. RP chromatographic separation of degradation species and C-terminal lysine variants along with the characterization of glycosylation profile by mass spectrometry demonstrates the capability of this method for whole antibody analysis. 相似文献
997.
998.
We consider the random matrix ensemble with an external sourcedefined on n×n Hermitian matrices, where A is a diagonal matrix with only two eigenvalues ±a of equal multiplicity. For the case a>1, we establish the universal behavior of local eigenvalue correlations in the limit n, which is known from unitarily invariant random matrix models. Thus, local eigenvalue correlations are expressed in terms of the sine kernel in the bulk and in terms of the Airy kernel at the edge of the spectrum. We use a characterization of the associated multiple Hermite polynomials by a 3×3-matrix Riemann-Hilbert problem, and the Deift/Zhou steepest descent method to analyze the Riemann-Hilbert problem in the large n limit.Dedicated to Freeman Dyson on his eightieth birthdayThe first author was supported in part by NSF Grants DMS-9970625 and DMS-0354962.The second author was supported in part by projects G.0176.02 and G.0455.04 of FWO-Flanders, by K.U.Leuven research grant OT/04/24, and by INTAS Research Network NeCCA 03-51-6637. 相似文献
999.
Let g=vect(M) be the Lie (super)algebra of vector fields on any connected (super)manifold M; let - be the change of parity functor, C
i
and H
i the space of i-chains and i-cohomology. The Nijenhuis bracket makes into a Lie superalgebra that can be interpreted as the centralizer of the exterior differential considered as a vector field on the supermanifold associated with the de Rham bundle on M. A similar bracket introduces structures of DG Lie superalgebra in L
* and for any Lie superalgebra g. We use a Mathematica-based package SuperLie (already proven useful in various problems) to explicitly describe the algebras l
* for some simple finite dimensional Lie superalgebras g and their relatives - the nontrivial central extensions or derivation algebras of the considered simple ones. 相似文献
1000.
We study classical trajectories corresponding to L=0 vibrations in the geometric collective model of nuclei with stable axially symmetric quadrupole deformations. It is shown that with increasing stability against the onset of triaxiality the dynamics passes between a fully regular and semiregular limiting regime. In the transitional region, an interplay of chaotic and regular motions results in complex oscillatory dependence of the regular phase space on the Hamiltonian parameter and energy. 相似文献