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溶解性有机质引发2,3-二溴丙基-2,4,6-三溴苯基醚光转化机理
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作者 张焱天 陈景文 +4 位作者 张亚南 崔飞飞 陈曦 郭忠禹 张思玉 《环境化学》 CAS CSCD 北大核心 2021年第9期2617-2628,共12页
光转化是水体中有机污染物的重要转化途径,决定污染物的环境暴露和风险.激发三线态溶解性有机质(^(3)DOM^(*))能够引发酚类、胺类和共轭二烯类污染物的间接光降解,反应机理涉及电子转移、质子转移和能量转移.然而,3DOM^(*)与新型溴代阻... 光转化是水体中有机污染物的重要转化途径,决定污染物的环境暴露和风险.激发三线态溶解性有机质(^(3)DOM^(*))能够引发酚类、胺类和共轭二烯类污染物的间接光降解,反应机理涉及电子转移、质子转移和能量转移.然而,3DOM^(*)与新型溴代阻燃剂(NBFRs)及具有类似结构的污染物的反应机理尚不清楚.本研究选取2,3-二溴丙基-2,4,6-三溴苯基醚(DPTE)为NBFRs模型化合物,以苯乙酮模拟DOM,通过光化学实验和密度泛函理论(DFT)计算,探究3DOM^(*)与NBFRs的反应活性、反应位点和反应途径.结果表明,激发三线态苯乙酮(^(3)AP^(*))对DPTE表观光降解的贡献为41.7%±2.2%,二者的二级反应速率常数为(1.49±0.24)×10^(8)L·mol^(-1)·s^(-1).DPTE的子结构模型化合物与苯乙酮的光化学实验表明,3AP^(*)与DPTE的反应位点为DPTE苯基上的溴.DFT计算表明,3AP^(*)通过向激发态DPTE转移电子使DPTE生成脱溴中间体,脱溴中间体与基态苯乙酮发生质子转移反应生成脱溴产物.所揭示的3AP^(*)引发DPTE光转化机理,有助于评价和预测水体中其他有溴代苯基醚结构的污染物光转化产物和动力学. 展开更多
关键词 溶解性有机质 新型溴代阻燃剂 光转化 激发态电子转移 光致质子转移
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Photophysical Properties of 4t-(p-aminophenyl)-2,2':6',2″-terpyridine
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作者 宋朋 孙士国 +3 位作者 周潘旺 刘建勇 徐勇前 彭孝军 《Chinese Journal of Chemical Physics》 SCIE CAS CSCD 2010年第5期558-564,622,共8页
Spectral and photophysical investigations of 4'-(p-aminophenyl)-2,2':6',2″-terpyridine (APT) have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra ... Spectral and photophysical investigations of 4'-(p-aminophenyl)-2,2':6',2″-terpyridine (APT) have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra of APT are found to exhibit dual fluorescence in polar solvents, which attributes to the local excited and intramolecular charge transfer states, respectively. The two-state model is proven out for APT in polar solvent by the time-correlated single photon counting emission decay measurement. Interestingly, the linear relationships of different emission maxima and solvent polarity parameter are found for APT in protic and aprotic solvents, because of the hydrogen bond formation between APT and alcohols at the amino nitrogen N25. Furthermore, the effects of the complexation of the metal ion with tpy group of APT and the hydrogen bond formation between APT with methanol at the terpyridine nitrogen N4-NS-N14 are also presented. The appearance of new long-wave absorption and fluorescence bands indicates that a new ground state of the complexes is formed. 展开更多
关键词 Dual fluorescence Local excited state Intramolecular charge transfer TERPYRIDINE COMPLEXATION Fluorescence decay
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Experimental and Theoretical Investigation on Excited State Intramolecular Proton Transfer Coupled Charge Transfer Reaction of Baicalein
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作者 胡闪闪 刘琨 +2 位作者 丁倩倩 彭伟 陈茂笃 《Chinese Journal of Chemical Physics》 SCIE CAS CSCD 2014年第1期51-56,I0003,共7页
The excited state intramolecular proton transfer (ESIPT) coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the ... The excited state intramolecular proton transfer (ESIPT) coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the absorption peak from S1 excited state both in the experi-mental and calculated absorption spectra indicates that S1 is a dark state. The dark excited state S1 results in the very weak fluorescence of solid baicalein in the experiment. The fron- tier molecular orbital and the charge difference densities of baicalein show clearly that the S1 state is a charge-transfer state whereas the S2 state is a locally excited state. The only one stationary point on the potential energy profile of excited state suggests that the ESIPT reaction of baicalein is a barrierless process. 展开更多
关键词 Excited state intramolecular proton transfer Intramolecular charge transfer Time-dependent density functional theory Dark state BAICALEIN
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High-lying excited states in ^10Be from the ^9Be(^9Be,^10Be)^8Be reaction
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作者 Wei Jiang YanLin Ye +24 位作者 ZhiHuan Li ChengJian Lin QiTe Li YuCheng Ge JianLing Lou DongXing Jiang Jing Li ZhengYang Tian Jun Feng Biao Yang ZaiHong Yang Jie Chen HongLiang Zang Qiang Liu PengJie Li ZhiQiang Chen Yun Zhang Yang Liu XiaoHui Sun Jing Ma HuiMing Jia XinXing Xu Lei Yang NanRu Ma LiJie Sun 《Science China(Physics,Mechanics & Astronomy)》 SCIE EI CAS CSCD 2017年第6期48-52,共5页
A transfer-reaction experiment of ~9Be(~9Be,^(10)Be)~8Be was performed at a beam energy of 45 Me V.Excited states in ^(10)Be up to 18.80 Me V are produced using missing mass and invariant mass methods.Most of the obse... A transfer-reaction experiment of ~9Be(~9Be,^(10)Be)~8Be was performed at a beam energy of 45 Me V.Excited states in ^(10)Be up to 18.80 Me V are produced using missing mass and invariant mass methods.Most of the observed high-lying resonant states,reconstructed from theα+~6He and t+~7Li decay channels,agree with the previously reported results.In addition,two new resonances at 15.6 and 18.8 Me V are identified from the present measurement.The 18.55 Me V state is found to decay into both the t + ~7Lig:s: and t + ~7Li?(0.478 MeV) channels, with a relative branching ratio of 0:93 ± 0:33. Further theoretical investigations are encouraged to interpret this new information on cluster structure in neutron-rich light nuclei. 展开更多
关键词 transfer reaction high-lying excited states cluster decay invariable mass method
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