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51.
52.
The electron spin polarization associated with electronic relaxation in molecules with trip-quartet and trip-doublet excited states is calculated. Such molecules typically relax to the lowest trip-quartet state via intersystem crossing from the trip doublet, and it is shown that when spin-orbit coupling provides the main mechanism for this relaxation pathway it leads to spin polarization of the trip quartet. Analytical expressions for this polarization are derived using first- and second-order perturbation theory and are used to calculate powder spectra for typical sets of magnetic parameters. It is shown that both net and multiplet contributions to the polarization occur and that these can be separated in the spectrum as a result of the different orientation dependences of the +/-1/2<-->+/-3/2 and +1/2<-->-1/2 transitions. The net polarization is found to be localized primarily in the center of the spectrum, while the multiplet contribution dominates in the outer wings. Despite the fact that the multiplet polarization is much stronger than the net polarization for individual orientations of the spin system, the difference in orientation dependence of the transitions leads to comparable amplitudes for the two contributions in the powder spectrum. The influence of this difference on the line shape is investigated in simulations of partially ordered samples. Because the initial nonpolarized state of the spin system is not conserved for the proposed mechanism, the net polarization can survive in the doublet ground state following electronic relaxation of the triplet part of the system. 相似文献
53.
The possibility of stimulating electron spin polarization in a system consisting of a stable paramagnetic center and a chromophore
that can be excited into its triplet state is discussed. In such systems, the doublet state of the paramagnetic center couples
to the excited triplet state of the chromophore and if the coupling is larger than the difference in the precession frequencies
of the doublet and triplet, the eigenstates of the coupled system are quartet and doublet states. The quartet state is usually
the lowest energy excited state. Following light excitation, the initial electronic relaxation to the quartet state generates
strong multiplet polarization if it is governed by the spin–orbit coupling that follows the molecular symmetry. It is shown
that application of a selective π-pulse to the ±3/2 ↔ ±1/2 transitions of the quartet converts this multiplet polarization
into net polarization. The magnitude and orientation dependence of the generated polarization is estimated on the basis of
a simple analytical model. The experimental conditions required for this net polarization to be retained in the ground state
after decay of the quartet state are discussed. The viability of using this as a method to enhance the signal strength of
a spin label or metal center in selective excitation experiments is considered. 相似文献
54.
Raquel G. Soengas Amalia M. Estévez Juan C. Estévez Ramón J. Estévez 《Tetrahedron: Asymmetry》2012,23(17):1238-1242
A novel strategy for the preparation of β,β′-dihydroxy α,α-disubstituted α-amino acids bearing a sugar moiety has been developed. The procedure is based on two Henry reactions: the first Henry reaction involves a sugar aldehyde and nitroethanol to furnish a sugar derived α-hydroxymethyl α-nitroalkanol while the second Henry reaction is between this nitro sugar and formaldehyde. This sequence provided the expected epimers of sugar derived α,α-dihydroxymethyl α -nitroalkanols, from which the corresponding β,β′-dibenzyloxy α-N-benzyloxycarbonylamino esters were easily obtained. All rights reserved. 相似文献
55.
The detection of singular points of DAEs is a challenging task, which has not been sufficiently considered so far. Combining automatic differentiation (AD) with the projector based analysis of DAEs, it becomes possible to monitor singularities while integrating the DAE. In this brief outline we restrict our considerations to linear DAEs. The corresponding treatment of nonlinear DAEs is based on linearization and can be found in the cited literature. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
56.
Terry Chu Lee Belding Prof. Dr. Art van der Est Prof. Dr. Travis Dudding Dr. Ilia Korobkov Dr. Georgii I. Nikonov 《Angewandte Chemie (International ed. in English)》2014,53(10):2711-2715
Reduction of the cationic GeII complex [dimpyrGeCl][GeCl3] (dimpyr=2,6‐(ArN=CMe)2NC5H3, Ar=2,6‐iPr2C6H3) with potassium graphite in benzene affords an air sensitive, dark green compound of Ge0, [dimpyrGe], which is stabilized by a bis(imino)pyridine platform. This compound is the first example of a complex of a zero‐valent Group 14 element that does not contain a carbene or carbenoid ligand. This species has a singlet ground state. DFT studies revealed partial delocalization of one of the Ge lone pairs over the π*(C?N) orbitals of the imines. This delocalization results in a partial multiple‐bond character between the Ge atom and imine nitrogen atoms, a fact supported by the X‐ray crystallography and IR spectroscopy data. 相似文献
57.
Laser flash-induced spin-polarized transient electron paramagnetic resonance (TREPR) spectra for bis(terpyridoxy)phosphorus(V) porphyrin in a nematic liquid crystal isotropic and in frozen solution are presented. At room temperature, two sequential spin-polarized TREPR spectra are observed. The first is consistent with the triplet state of a radical pair, while the later is assigned to the triplet state of the porphyrin formed by charge recombination. On the basis of the spectroscopic and redox properties of the terpyridine and porphyrin moieties it is proposed that electron transfer from the terpyridine to the excited phosphorus(V) porphyrin occurs. The lifetime of the radical pair is estimated to be of about 175 ns. At low temperature, the radical pair spectrumis no longer observed and the spin polarization pattern of the porphyrin triplet is dramatically different. This behavior is explained by postulating that the electron transfer is inhibited at low temperature because molecular motion is required to stabilize the radical pair. It is proposed that in the absence of this stabilization, the porphyrin triplet state is populated via spin-orbit coupling-mediated intersystem crossing from the excited singlet state. 相似文献
58.
We present a generalization of the singular manifold method for equations with two branches in the Painlevé expansion. The method is applied to the modified Korteweg-de Vries equation. The connection with Hirota's bilinear formalism is also established.Area de Física Teórica. Facultad de Ciencias, Universidad de Salamanca, 37008 Salamanca, Spain. Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 99, No. 3, pp. 370–376, June, 1994. 相似文献
59.
We develop a generalized conditional symmetry approach for the functional separation of variables in a nonlinear wave equation with a nonlinear wave speed. We use it to obtain a number of new (1+1)-dimensional nonlinear wave equations with variable wave speeds admitting a functionally separable solution. As a consequence, we obtain exact solutions of the resulting equations. 相似文献
60.
Wang L Estévez MC O'Donoghue M Tan W 《Langmuir : the ACS journal of surfaces and colloids》2008,24(5):1635-1639
In this paper, we report the preparation and characterization of fluorophore-free luminescent organosilica nanoparticles (NPs) with sizes varying from 50 to 250 nm. These NPs were synthesized by the St?ber method by incorporating several organosilanes together with the silicate precursor (tetraethyl orthosilicate, TEOS) to the silica matrix. The calcination of these NPs at high temperatures (600 and 700 degrees C) led to fluorescent and phosphorescent properties, which proved to be highly dependent on the initial composition of the silanization mixture and the heating temperature. Further characterization of this material in terms of its structural and optical properties is reported. Although the NPs are not very bright, the lifetime measurements revealed values in the millisecond range, which makes these NPs potentially attractive as luminescent materials and for time-resolved optical spectroscopic studies and bioassays. 相似文献