CCl2(A 1B 1,a3B1)自由基被烷烃类分子猝灭动力学

用放电 LIF实验装置,对CCl4/Ar混合气体放电产生CCl2自由基,再用541.52 nm激光将电子基态CCl2激励到激发态A 1B1(0,4,0)振动能级上,通过检测激发态CCl2时间分辨荧光信号,测得室温下CCl2(A 1B1)被烷烃类分子猝灭的实验结果,用我们提出的三能级模型分析处理实验数据,获得CCl2(A 1B1)态和CCl2(a 3B1)态的碰撞猝灭速率常数kA和ka值.     

脉冲直流放电-LIF法CCl2(A1B1和a3B1)自由基被醇类分子猝灭动力学研究

CCl4/Ar混合气体进行脉冲高压直流放电产生CCl2自由基,再用YAG泵浦的染料激光输出的541.52 nm激光将电子基态CCl2激励到电子激发态A1B1(0,4,0)模的pR1能级上,通过检测激发态CCl2自由基的时间分辨荧光信号,测得了室温下(293 K)激发态CCl2自由基被醇类分子猝灭的动力学结果,根据我们提出的三能级模型来分析处理这些实验数据,首次获得了激发态CCl2自由基被醇类分子猝灭的态分辨的速率常数kq1,kq2和kq3的值.并对这些数据与猝灭剂的结构关系进行了分析讨论.     

CCl2自由基被无机小分子猝灭的速率常数

对CCl4/Ar混合气体脉冲直流高压放电产生CCl2自由基,用541.52 nm激光将电子基态CCl2激励到A 1B1(0,4,0)振动能级上. 通过检测激发态CCl2时间分辨荧光信号,测得室温下CCl2(A 1B1和a 3B1)被O2、N2、NO、 CO2、 CS2、H2O、SO2,和SF6分子猝灭的实验结果.用我们提出的三能级模型分析处理实验数据,获得了CCl2(A 1B1)态和CCl2(a 3B1)态的碰撞猝灭速率常数kA和ka值.     

CCl2(A1B1和a3B1)被酮类分子猝灭速率常数的测定

对CCl4/Ar混合气体脉冲直流高压放电产生CCl2自由基,经过约110μs后,再用541.52mm激光将电子基态CC2激励到激发态A1B1(0,4,0)振动态K=0能级上,通过检测激发态CCl2(A)时间分辨荧光信号,测得室温下CC2(A1B1和a3B1)被酮类分子猝灭的实验结果,用所提出的三能级模型分析处理实验数据,获得态分辨速率常数KA和Ka值.     

胶束电动色谱法测定五维他口服溶液中维生素B_1、B_2、B_6、烟酰胺、泛酸钙与苯甲酸钠

建立了胶束电动色谱(MEKC)法通过波长切换同时测定五维他口服溶液中的维生素B_1、B_2、B_6、烟酰胺、泛酸钙及苯甲酸钠含量的方法,并优化了检测波长、十二烷基硫酸钠(SDS)的浓度、分离电压、缓冲液浓度及pH值等实验条件。最佳分离条件为以未涂渍的标准熔融石英毛细管柱(75μm×50 cm,有效长度42 cm)为分离通道;40 mmol/L硼酸+40 mmol/L硼砂+20 mmol/L SDS(pH 9.0)为运行缓冲液,分离电压20 kV,柱温25℃,检测波长为270 nm(维生素B_1、B_2、B_6、烟酰胺及苯甲酸钠)和200 nm(泛酸钙),电动进样10 kV、进样时间10 s。结果显示,6种化合物可在13 min内实现基线分离,且在一定质量浓度范围内线性良好,相关系数(r)不小于0.998 9;3个加标水平下的平均回收率为97.0%～103%,RSD为0.60%～1.8%。该方法快速、准确,可用于五维他口服溶液中维生素B_1、B_2、B_6、烟酰胺、泛酸钙及苯甲酸钠的含量测定。     

CCl2(A1B1)被甲烷及氯代甲烷猝灭动力学

用放电-LIF实验装置,对CCl4/Ar混合气体放电产生*CCl2,再用541.52nm激光将电子基态*CCl2激发到激发态A1B1(0,4,0)模pR1能级上,检测激发态*CCl2时间分辨荧光信号,测得室温下*CCl2(A1B1)被甲烷及氯代甲烷分子猝灭的实验结果,用三能级模型分析处理实验数据获得态分辨速率常数kq1,kq2和kq3值和*CCl2(A1B1→X1A1)及(a3B1→X1A1)自发辐射寿命分别为(0.83±0.03)μs和(3.12±0.25)μs.     

CCl2(A^1B1)自由基不同振动态的猝灭动力学

对CCl4/Ar混合气体直流脉冲放电产生CCl2自由基，再分别用波长为550.56nm,541.52nm,532.25nm,524.31nm,523.82nm和523.27nm的激光将电子基态CCl2激励到激发态A^1B1的(0,3,0),(0,4,0),(1,3,0),(0,6,0),(1,4,0),(2,2,0)振动态，激发态CCl2(A^1B1)的不同振动态的时间分辨荧光信号显示该信号呈双指数衰减，测得室温下CCl2(A^1B1)不同振动态被NH3,H2O,CH2Br2,NH(CH3)2,NH(C2H5)2,N(C2H5)3,n-C6H14等分子猝灭的实验结果，用三能级模型分析处理实验数据，获得态分辨速率常数kA和ka值，并对实验结果进行了讨论。     

脉冲直流放电-LIF法CCl~2(A'B~1和a^3B~1)自由基被醇类分子 猝灭动力学研究

CCl~4/Ar混合气体进行脉冲高压直流放电产生CCl~2自由基,再用YAG泵浦的染料激光输出的541.52nm激光将电子基态CCl~2激励到电子激发态A^1B~1(0,4,0)模的P^R~1能级上,通过检测激发态CCl~2自由基的时间分辨荧光信号,测得了室温下(293K)激发态CCl~2自由基被醇类分子猝灭的动力学结果,根据我们提出的三能级模型来分析处理这些实验数据,首次获得了激发态CCl~2自由基被醇类分子猝灭的态分辨的速率常数k~q~1,k~q~2和k~q~3的值,并对这些数据与猝灭剂的结构关系进行了分析讨论。     

脉冲直流放电-LIF法CCl~2(A'B~1和a^3B~1)自由基被醇类分子 猝灭动力学研究

CCl~4/Ar混合气体进行脉冲高压直流放电产生CCl~2自由基,再用YAG泵浦的染料激光输出的541.52nm激光将电子基态CCl~2激励到电子激发态A^1B~1(0,4,0)模的P^R~1能级上,通过检测激发态CCl~2自由基的时间分辨荧光信号,测得了室温下(293K)激发态CCl~2自由基被醇类分子猝灭的动力学结果,根据我们提出的三能级模型来分析处理这些实验数据,首次获得了激发态CCl~2自由基被醇类分子猝灭的态分辨的速率常数k~q~1,k~q~2和k~q~3的值,并对这些数据与猝灭剂的结构关系进行了分析讨论。     

CCl2(A1B1)被O2及取代甲烷类分子猝灭的动力学研究

对CCl4／Ar混合气体放电产生CCl2自由基，再用541.52nm激光将电子基态CCl2激发到激发态A^1B1（0，4，0）振动态k=0能级上，通过检测 激发态CCl2时间分辨荧光信号，测得室温下CCl2(A^1B1)被O2，CF4，CF2Cl，CH3NO2，CH2Br2等分子猝灭的实验结果，用改进的三能级模型分析处理实验数据，获得态分辨速常数KA和Ka值，并对实验结果进行了讨论。     

CCl_2自由基被无机小分子猝灭的速率常数

对ＣＣｌ４／Ａｒ混合气体脉冲直流高压放电产生 ＣＣｌ２自由基,用 ５４１．５２ ｎｍ激光将电子基态 ＣＣｌ２激励到Ａ１Ｂ１（０,４,０）振动能级上．通过检测激发态 ＣＣｌ２时间分辨荧光信号,测得室温下 ＣＣｌ２（Ａ１Ｂ１和 ａ３Ｂ１）被 Ｏ２、Ｎ２、ＮＯ、ＣＯ２、ＣＳ２、Ｈ２Ｏ、ＳＯ２,和ＳＦ６分子猝灭的实验结果．用我们提出的三能级模型分析处理实验数据,获得了ＣＣｌ２（Ａ１Ｂ１）态和 ＣＣｌ２（ａ３Ｂ１）态的碰撞猝灭速率常数 ｋＡ和 ｋａ值．     

A combined ab initio/Franck-Condon study of the A-X single-vibronic-level emission spectrum of CCl2 and the photodetachment spectrum of CCl2 -.

State-of-the-art ab initio calculations have been carried out on the X1A1, ?3B1 and A1B1 states of CCl2 and the X2B1 state of CCl2-. Franck-Condon factors including anharmonicity have been calculated, between the CCl2 states, and between the CCl2- X2B1 state and the CCl2 states. They are used to simulate the A-X single-vibronic-level (SVL) emission spectra of CCl2 determined by M.-L. Lui et al. [PCCP 2003, 5, 352] and the 364 nm laser photodetachment spectrum of CCl2- obtained by R. L. Schwartz et al. [J. Phys. Chem. A 1999, 103, 8213]. Comparison between simulated and observed spectra confirms the vibrational assignments of the X2B1 SVL emission spectra and the T0 position of the A1B1 state of CCl2. For the photodetachment spectrum of CCl2-, spectral simulation shows that the higher binding energy ?3B1(CCl2) <-- X2B1(CCl2-) band is well separated from the X1A1(CCl2) <-- X2B1(CCl2-) band. It is concluded that the observed second band, which overlaps heavily with the X1A1(CCl2) <-- X2B1(CCl2-) band in the photodetachment spectrum of CCl2- cannot be assigned to the CCl2(?3B1) + e --> CCl2-(X2B1) detachment process. Further ab initio calculations carried out in the present investigation support the suggestion that the second band in the 364 nm photodetachment spectrum of CCl2- is due to detachment from an excited state of CCl2-, a linear quartet state, to a triplet state of CCl2. These calculations identify the anionic state to be the lowest 4Sigmag- (4Sigma-) state, which photodetaches vertically to the 3Sigmag- (3Sigma-; adiabatically ?3B1) and/or 3Pi(u) (3Pi) states of CCl2 to give the second band observed in the 364 nm photodetachment spectrum of CCl2-.     

Solvent‐Free Photooxidation of Alkanes by Dioxygen with 2,3‐Dichloro‐5,6‐dicyano‐p‐benzoquinone via Photoinduced Electron Transfer

Photooxidation of alkanes by dioxygen occurred under visible light irradiation of 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) which acts as a super photooxidant. Solvent‐free hydroxylation of cyclohexane and alkanes is initiated by electron transfer from alkanes to the singlet and triplet excited states of DDQ to afford the corresponding radical cations and DDQ^??, as revealed by femtosecond laser‐induced transient absorption measurements. Alkane radical cations readily deprotonate to produce alkyl radicals, which react with dioxygen to afford alkylperoxyl radicals. Alkylperoxyl radicals abstract hydrogen atoms from alkanes to yield alkyl hydroperoxides, accompanied by regeneration of alkyl radicals to constitute the radical chain reactions, so called autoxidation. The radical chain is terminated in the bimolecular reactions of alkylperoxyl radicals to yield the corresponding alcohols and ketones. DDQ^??, produced by the photoinduced electron transfer from alkanes to the excited state of DDQ, disproportionates with protons to yield DDQH₂.     

State‐state transitions for CCl2(X1A1, A1B1, a3B1) radical and collisional quenching of CCl2(A1B1 and a3B1) by O2, N2, NO,N2O,NH3, and various aminated molecules

CCl₂ free radicals were produced by a pulsed dc discharge of CCl₄ in Ar. Ground electronic state CCl₂(X) radicals were electronically excited to the A¹B₁ (0,4,0) vibronic state with an Nd:YAG laser pumped dye laser at 541.52 nm. Experimental quenching data of excited CCl₂(A¹B₁ and a³B₁) by O₂, N₂, NO, N₂O, NH₃, NH(CH₃)₂, NH(C₂H₅)₂, and N(C₂H₅)₃ molecules were obtained by observing the time‐resolved total fluorescence signal of the excited CCl₂ radical in a cell, which showed a superposition of two exponential decay components under the presence of quencher. The quenching rate constants k_A of CCl₂(A) state and k_a of CCl₂(a) state were derived by analyzing the experimental data according to a proposed three‐level model to deal with the CCl₂(X¹A₁, A¹B₁, a³B₁) system. The formation cross sections of complexes of electronically excited CCl₂ radicals with O₂, N₂, NO, N₂O, NH₃, and aminated molecules were calculated by means of a collision‐complex model. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 351–356, 2002