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1.
An X-band EPR study on a Na_3(CrMo_6O_(24)H_6)·8H_2O single crystal diluted by its isomor-phic compound Na_3(AlMo_6O_(24)H_6)·8H_2O at room temperature is reported. Using the least squares-fitting method to simulate the EPR data for principal planes, the Hamiltonian parameterswere obtained. The principal values of the g tensors are g_(ZZ) = 1.904, g_(XX)= 1.973, g_(YY)=1.933. The zero field splitting tensor parameters are D = 0.275 cm~(-1), E = 0.05 cm~(-1). The fielddependence of Cr~(3+) energy levels with field at different angles from the principal axes whenthe field is along the principal planes is calculated based on these experimental parameters.The isofrequency plots of calculated field vs. angle are also shown. They agree well with theexperimental results. 相似文献
2.
Subhasis Chakrabarti Ashim K. Maity T. N. Misra 《Journal of polymer science. Part A, Polymer chemistry》1992,30(8):1625-1631
Raman spectroscopy has been used to study solid-state photopolymerization reactions in dimethyl ester of α,α′-dicyano-p-phenylenediacrylic acid (p-CPAMe) and diethyl ester of p-phenylenediacrylic acid (p-PDAEt). The reactants and products were characterized by infrared and Raman spectroscopy. Excitation and emission spectra suggest that in p-CPAMe exciton–phonon coupling is strong, but in the other monomer it is very weak. Raman phonon spectroscopic study reveal that in both the samples the reaction mechanism is homogeneous in the initial stages. However, in the later stages the reaction becomes heterogeneous in p-PDAEt. In p-CPAMe the lattice becomes disordered with the progress of polymerization and finally becomes amorphous whereas in p-PDAEt the lattice remains highly ordered. © 1992 John Wiley & Sons, Inc. 相似文献
3.
Raman phonon spectroscopy has been used to study photodimerization reaction inp-chloro cinnamic acid (pCCA) crystal. The β-form of the crystal yields the 4,4′-dichloro-β-truxinic acid dimer. Six distinct low frequency phonon
bands are observed in thepCCA monomer crystal. On reaction progress, these bands show a monotonic shift to lower frequencies and broaden out. Finally,
in the dimer crystal the phonon spectrum shows two weak broad bands. These results suggest that the reaction is homogeneous
in the initial stages and, as the product concentration increases, the lattice becomes highly disordered. The reactant and
the product were characterised by infrared and Raman spectroscopy. The disappearance of aliphatic C=C bond stretching vibration
and appearance of cyclobutane ring deformation and cyclobutane ring-breathing vibrations on reaction confirm photodimerization
by cyclobutane ring formation. The large Stoke's shift between the absorption and emission band suggest strong exciton-phonon
coupling in the monomer lattice. This reaction seems to be phonon-mediated. 相似文献
4.
溶液中光诱导的电子转移反应已进行了大量的研究。而半导体粉末在水相或非水溶剂中的光化学研究也与自俱增[1-3]。这种光化学与成像体系、太阳能转换以及光催化或污物的光降解有关。因此,越来越引起人们的重视。 相似文献
5.
本文研究了乙酰基香豆素及其衍生物与吲哚的混晶在微环境影响下的固相光反应,并用固体紫外光谱、固体荧光光谱和X-射线粉末衍射技术考察了混晶的特征。实验结果表明,3-乙酰基香豆素及其7-乙酰氧基、7-苯甲酰氧基、5,6-苯并和6-溴衍生物与吲哚的固相光反应分别得到1:2缩合产物1~5,而6-硝基衍生物与吲哚的固相光反应却得到开环脱羰加成产物6。通过IR、MS、^1H NMR和元素分析结果确定了这六个新产物的结构。固体光谱的测试结果表明,取代乙酰基香豆素与吲哚间混晶的形成,分子间存在相互作用,使分子所处的微环境条件发生了变化。 相似文献
6.
7.
应用从头算分子轨道法分别在RHF/6-31G**和UHF/6-31G**水平上对3腔┤┓肿拥幕?S0)和三重激发态(T1)单键旋转异构反应机理进行了研究,优化出反应物和产物在S0态和T1态的4种平衡态和过渡态的几何构型,通过振动分析得到的虚频和计算的内禀反应坐标对过渡态进行了确认,并得到了零点能,根据基态和激发态反应途径分析了光反应机理。计算结果表明,基态和激发态的3腔┤┓肿拥ゼ旃狗从ξ焕萁系停嘏湃菀追⑸永砺凵涎橹ち斯夥从κ笛橹屑钢忠旃固宓拇嬖凇? 相似文献
8.
Xun Chen Lie Chen Yiwang Chen 《Journal of polymer science. Part A, Polymer chemistry》2013,51(19):4156-4166
Three different types of photocrosslinkable groups into a low band‐gap donor–acceptor‐conjugated polymer, namely poly{benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐ thieno[3,4‐b]thiophene} (PBT), were developed to comparatively investigate the effect of the photocrosslinkable groups on the thermal stability of bulk heterojunction solar cells. Compared with vinyl groups, bromine‐ and azide‐ photocrosslinkable groups are more prompt for photocrosslinking to yield a denser crosslinking network, probably due to the different crosslinking mechanisms and reaction rates. In contrast to the reference device decreasing to less than 10% of its initial efficiency value after 80 h of annealing at 150 °C, a great improvement in the thermal stability of performance of all these crosslinked functional copolymers devices demonstrates that photocrosslinking can effectively improve the thermal stability of the active layer by suppressing [6,6]‐phenyl‐C61‐butyric acid methyl diffusion and phase separation. Furthermore, the solar cells with crosslinked bromine‐ and azide‐functionalized PBT polymers showed very thermally stable photovoltaic device performance by retaining 78 and 66% of their initial device efficiency, respectively, whereas vinyl‐functionalized PBT devices retained only 51% of its initial value after long‐time thermal annealing. This suggests that an appropriate crosslinking network with homogenous active morphology could dramatically enhance the device stability without sacrificing the performance. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4156–4166 相似文献
9.
由于半导体超微粒子具有独特的尺寸量子化效应和表面效应[1~6],它在利用太阳能光催化降解有机污染物,有机光合成及光电转化等领域中有着极其广泛的应用.目前,大量的工作集中在超微颗粒表面上有机物的光反应过程的研究[7]. 相似文献
10.
Nobuhiro Kawatsuki Imin Sai Tohei Yamamoto 《Journal of polymer science. Part A, Polymer chemistry》1999,37(21):4000-4006
We present (1) the linearly polarized (LP) ultraviolet (UV) photoreaction of block copolyesterethers comprising a hard segment of polyester and soft segment of poly(tetramethylene ether) (PTMG) and (2) the alignment behavior of liquid crystals (LCs) on the resultant photoreacted polymer films. Two kinds of copolyesterethers with different polyester segments of poly(hexamethylene p-phenylenediacrylate) (1a) or poly(hexamethylene p-phenylenediacrylate)-co-poly(hexamethylene 1,4-dibenzoate) (1b) were used in this study. The LP–UV irradiation resulted in a negative optical anisotropy for both polymer films, and a homogeneous photoalignment of LCs was achieved on the photoreacted polymer film. The LC alignment was perpendicular to the electric vector of the incident polarized light for 1a, whereas a reversion of the alignment from parallel to perpendicular was observed for 1b, depending on the irradiation doses. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4000–4006, 1999 相似文献