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901.
The signatures of nanosolvation on the one‐ and two‐dimensional (1D and 2D) IR spectra of a proton‐transfer mode in a hydrogen‐bonded complex dissolved in polar solvent molecule nanoclusters of varying size are elucidated by using mixed quantum–classical molecular dynamics simulations. For this particular system, increasing the number of solvent molecules successively from N=7 to N=9 initiates the transition of the system from a cluster state to a bulk‐like state. Both the 1D and 2D IR spectra reflect this transition through pronounced changes in their peak intensities and numbers, but the time‐resolved 2D IR spectra also manifest spectral features that uniquely identify the onset of the cluster‐to‐bulk transition. In particular, it is observed that in the 1D IR spectra, the relative intensities of the peaks change such that the number of peaks decreases from three to two as the size of the cluster increases from N=7 to N=9. In the 2D IR spectra, off‐diagonal peaks are observed in the N=7 and N=8 cases at zero waiting time, but not in the N=9 case. It is known that there are no off‐diagonal peaks in the 2D IR spectrum of the bulk version of this system at zero waiting time, so the disappearance of these peaks is a unique signature of the onset of bulk‐like behavior. Through an examination of the trajectories of various properties of the complex and solvent, it is possible to relate the emergence of these off‐diagonal peaks to an interplay between the vibrations of the complex and the solvent polarization dynamics. 相似文献
902.
Dr. Sylvain Achelle Dr. Jean‐Pierre Malval Dr. Stéphane Aloïse Dr. Alberto Barsella Dr. Arnaud Spangenberg Dr. Loic Mager Dr. Huriye Akdas‐Kilig Dr. Jean‐Luc Fillaut Prof. Bertrand Caro Prof. Françoise Robin‐le Guen 《Chemphyschem》2013,14(12):2725-2736
The nonlinear properties and the photophysical behavior of two π‐conjugated chromophores that incorporate an electron‐deficient pyrimidine core (A) and γ‐methylenepyrans as terminal donor (D) groups have been thoroughly investigated. Both dipolar and quadrupolar branching strategies are explored and rationalized on the basis of the Frenkel exciton model. Even though a cooperative effect is clearly observed if the dimensionality is increased, the nonlinear optical (NLO) response of this series is moderate if one considers the nature of the D/A couple and the size of the chromophores (as measured by the number of π electrons). This effect was attributed to a disruption in the electronic conjugation within the dyes’ scaffold for which the geometry deviates from planarity owing to a noticeable twisting of the pyranylidene end‐groups. This latter structural parameter also has a strong influence on the excited‐state dynamics, which leads to a very efficient fluorescence quenching. 相似文献
903.
Dr. Adrien Bourdolle Dr. Mustapha Allali Dr. Anthony D'Aléo Dr. Patrice L. Baldeck Dr. Kenji Kamada Prof. J. A. Gareth Williams Dr. Hubert Le Bozec Dr. Chantal Andraud Dr. Olivier Maury 《Chemphyschem》2013,14(14):3361-3367
The synthesis of tris(2‐thenoyltrifluoroacetonate)lanthanide(III) complexes featuring a diethylaminostyryl‐2,2′‐bipyridine coligand was achieved for lanthanum; the near‐infrared (NIR) emitters neodymium, erbium, and ytterbium; and the transition‐metal yttrium. The photophysical properties were thoroughly studied, and it was demonstrated that the conjugated bipyridine ligand acts as a good antenna for the sensitization of the NIR emitters. The two‐photon absorption (TPA) properties of all five complexes were investigated by using both two‐photon excited fluorescence and the Z‐scan method. We demonstrate that the nature of the rare earth ion has almost no influence on the TPA properties centered on the conjugated bipyridyl ligand. Finally, we show that YbIII is sensitized by a two‐photon antenna effect, and that NdIII is mostly sensitized by a one‐photon process involving direct excitation of forbidden f–f transitions. 相似文献
904.
金属有机骨架(MOFs)材料因其可设计的结构以及灵活可控的配位模式,在三阶非线性光学(NLO)领域引起了广泛的关注。与液体分散状态相比,MOFs在固体状态下的三阶NLO性能更为重要,这不仅可以深入了解MOFs本身所固有的光学性能,还有助于实现MOFs在光学器件中的实际应用。然而,由于散射的存在和透光率的限制,单独的MOFs材料难以直接实现固体状态下的三阶NLO性能研究,将MOFs制备成具有较好光学透过性的薄膜是研究其NLO性能最为可行的一种策略。MOFs薄膜不仅很好地继承了MOFs所固有的三阶NLO性能,而且还结合了薄膜的高透光率以及灵活的机械性能。基于此,本文分析总结了MOFs薄膜的制备方法及其NLO性能研究方面的相关工作,并根据目前MOFs薄膜在三阶NLO性能方面的研究现状对其未来发展予以了展望。 相似文献
905.
《高分子科学杂志,C辑:聚合物评论》2013,53(2):99-124
Thermally stimulated recovery (TSR) is a non‐conventional mechanical spectroscopy technique that allows to analyse in detail the relaxation processes of polymeric systems in the low frequency region. This work reviews the main aspects and potentialities of this technique. The different kinds of TSR experiments that can be performed, global and thermal sampling (TS) experiments, are described and illustrated with several examples. Also, the different methods for the determination of the thermokinetic parameters (activation energy and pre‐exponential factor) of the thermal sampling (TS) procedure are explained and compared. In this context, the compensation phenomenon, which always appears in TSR results when the studies are performed in the glass transition region of a given system, is discussed. Examples of the application of this technique to different polymeric systems during the last 20 years are provided. An emphasis will be made on the analysis of the effect of crystallinity degree and crosslink density on the TSR response. A comparison between the results (characteristic times and activation energies) obtained by different techniques, namely TSR, dynamic mechanical analysis (DMA), and differential scanning calorimetry (DSC), is made. 相似文献
906.
酸催化溶胶-凝胶法制备高强度SiO2增透膜研究进展 总被引:1,自引:0,他引:1
高强度增透膜是用于减少表面反射、增加光线透光率的薄膜,具有密度低、折射率可调、耐磨性好的特点.本文综述了高强度增透膜的制备方法与研究进展,介绍了酸催化溶胶-凝胶法制备SiO2溶胶的机理及影响因素,酸催化溶胶-凝胶法及两种辅助酸催化溶胶-凝胶法制备高强度增透膜的方法,对高强增透膜制备的发展方向和应用前景进行了展望. 相似文献
907.
Silacyclophanes possessing two disilanyl pillars were synthesized from tricyclic heteroarenes in one‐pot synthetic procedures. The step‐like anti structures of three congeners bearing two heteroarene units were revealed in single crystals by X‐ray crystallographic analysis. Depending on the structures of aromatic units, torsion angles at the disilanyl pillars altered to maintain the overall step‐like molecular structures. The structure, however, fluctuated between anti and syn conformers in a solution phase despite the presence of eight methyl groups on the ring periphery. The analysis of the coalescence temperature with NMR spectroscopy showed the fundamental energetics of the dynamics. The subtle structural differences affected the dynamic behavior of the silacyclophanes. 相似文献
908.
Hua‐Wei Li Sabyasachi Kar Pinghui Jiang 《International journal of quantum chemistry》2013,113(10):1493-1497
The effects of Debye plasma on the frequency‐dependent polarizabilities of Li and Na atoms are investigated using symplectic algorithm within the framework of the pseudostate summation technique. Dynamic dipole polarizabilities of Li (2s 2S) and Na(3s 2S) as functions of scaled number density of the plasma electrons for arbitrary plasma temperature are presented. Screening effects on the resonance frequencies are also presented. In free‐atomic cases, our calculated results are comparable with the reported theoretical and experimental predictions. © 2012 Wiley Periodicals, Inc. 相似文献
909.
Andrea Fülöpová Peter Magdolen Miroslava Károlyiová Ivica Sigmundová Pavol Zahradník 《Journal of heterocyclic chemistry》2013,50(3):563-567
A six‐step synthesis of the unsymmetrical trimethylbenzotristhiazole has been developed. Starting from 2‐methylbenzothiazole following nitration, reduction, acetylation, thionation, and twofold cyclization, the desired trimethylbenzotristhiazole was obtained in good yield. Its condensation with donor‐substituted benzaldehydes presents the way to new octupolar chromophores. The attempt to synthesize such benzotristhiazole from dinitroaniline failed; this procedure afforded a new benzimidazole derivative. 相似文献
910.
A water-soluble derivative of chitosan, carboxymethylchitosan (CMCH), was mixed with alkyltrimethylammoniumbromides (CmTAB) and was studied on the adsorption at air/water interface using equilibrium and dynamic surface tension method. The effects of surfactant and polymer concentrations, surfactant chain length, as well as pH of solution were investigated. Addition of the surfactants remarkably promotes the polymer adsorption. Increasing any one of surfactant concentration, surfactant chain length, and pH will facilitate the adsorption of the mixture whereas little effects of polymer concentration were observed. The results are explained in terms of the interaction between CMCH and CmTAB under different conditions. 相似文献