Charge transport properties of F, OH, OCH3, SH and SCH3-substituted tetra- benz[a,c,h,j]- anthracene derivative molecules have been investigated theoretically at the B3LYP/6-31G＊＊ level using Marcus theory. The resu...Charge transport properties of F, OH, OCH3, SH and SCH3-substituted tetra- benz[a,c,h,j]- anthracene derivative molecules have been investigated theoretically at the B3LYP/6-31G＊＊ level using Marcus theory. The results showed that at 300 K, the hole or electron transport capability of F or SH-substituted molecules was better obviously than that of OH or OCH3-substituted molecules, The electron transport capability of SCH3-substituted and F or SH-substituted molecules was superior to their hole transport capability, respectively. F, SH or SCH3-substituted tetrabenz[a,c,h,j]-anthracene derivative molecules can be used as electron transport materials.展开更多
Humic acid is a key component of extracellular electron acceptor. Experimental study elucidates that humic acid molecular ligand with different metal elements has different abilities to accept electrons. By using dens...Humic acid is a key component of extracellular electron acceptor. Experimental study elucidates that humic acid molecular ligand with different metal elements has different abilities to accept electrons. By using density functional theory, this article selected the leonardite humic acid(LHA) organic macromolecule as ligand to study interactions between the ligand and different metals. At the same time, the calculation of binding energy, the analysis of characteristics for the complex structure and the distribution of frontier molecular orbital were also completed. On the basis of Marcus theory, the reorganization energy, matrix element and charge transport rate constant were calculated. The results show that the order of the charge transfer rates is Fe^(3+)>Cu^(2+)>Al^(3+) for different metal complexes, and are in good agreement with the experimental ones.展开更多
The oxidation of Na4Fe(CN)6 complex by S2O8 2- anion was found to follow an outer-sphere electron transfer mechanism. We firstly carried out the reaction at pH=1. The specific rate constants of the reaction...The oxidation of Na4Fe(CN)6 complex by S2O8 2- anion was found to follow an outer-sphere electron transfer mechanism. We firstly carried out the reaction at pH=1. The specific rate constants of the reaction, kox, are (8.1± 0.07)×10-2 and (4.3±0.1)×10-2 mol-1?L?s-1 at μ=1.0 mol?L-1 NaClO4, T=298 K for pH=1 (0.1 mol?L-1 HClO4) and 8, respectively. The activation parameters, obtained by measuring the rate constants of oxidation 283—303 K, were ?H≠=(69.0±5.6) kJ?mol-1, ?S≠=(-0.34±0.041)×102 J?mol-1?K-1 at pH=1 and ?H≠= (41.3±5.5) kJ?mol-1, ?S≠=(-1.27±0.33)×102 J?mol-1?K-1 at pH=8, respectively. The cyclic voltammetry of Fe(CN)36 -/4- shows that the oxidation is a one-electron reversible redox process with E1/2 values of 0.55 and 0.46 V vs. normal hydrogen electrode at μ=1.0 mol?L-1 LiClO4, for pH=1 and pH=8 (Tris), respectively. The kinetic results were discussed on the basis of Marcus theory.展开更多
Electron transfer reactions take place readily between 2, 2, 6, 6-tetramethylpiperidine oxoammonium ions (la,lb) and phenothiazines (2a—2g), giving corresponding nitroxides (3a,3b) and phenothiazine radical cations ...Electron transfer reactions take place readily between 2, 2, 6, 6-tetramethylpiperidine oxoammonium ions (la,lb) and phenothiazines (2a—2g), giving corresponding nitroxides (3a,3b) and phenothiazine radical cations (4a—4g). The rate constants for the electron self-exchange reactions between1 and3, as well as between2 and4, are determined by EPR and1HNMR line-broadening effect in acetonitrile. By application of the Marcus theory, the kinetics of the cross exchange reactions between1 and2 is studied.展开更多
The fluorescence of gramicidin A(GA) in lipid bilayer may be quenched by Hypocre-Ilin B. When the phospholipids undergo a phase transition from gel to liquid crystalline phase, the reaction rate decreases unusually. T...The fluorescence of gramicidin A(GA) in lipid bilayer may be quenched by Hypocre-Ilin B. When the phospholipids undergo a phase transition from gel to liquid crystalline phase, the reaction rate decreases unusually. This phenomenon has been analyzed by Marcus’ pho-toinduced electron theory, and an electron transfer inverted region hypothesis is proposed,展开更多
基金sponsored by the National Natural Science Foundation of China(No.50973076)Sichuan Provincial Scientific Program(No.2010JY0041 and 2011ZG0247)the Natural Science Program of Sichuan Provincial Education Department(No.11ZA206)
文摘Charge transport properties of F, OH, OCH3, SH and SCH3-substituted tetra- benz[a,c,h,j]- anthracene derivative molecules have been investigated theoretically at the B3LYP/6-31G＊＊ level using Marcus theory. The results showed that at 300 K, the hole or electron transport capability of F or SH-substituted molecules was better obviously than that of OH or OCH3-substituted molecules, The electron transport capability of SCH3-substituted and F or SH-substituted molecules was superior to their hole transport capability, respectively. F, SH or SCH3-substituted tetrabenz[a,c,h,j]-anthracene derivative molecules can be used as electron transport materials.
基金supported by the Sichuan Province Department Education(13ZA0150)the Sichuan Province(2014JY0099)
文摘Humic acid is a key component of extracellular electron acceptor. Experimental study elucidates that humic acid molecular ligand with different metal elements has different abilities to accept electrons. By using density functional theory, this article selected the leonardite humic acid(LHA) organic macromolecule as ligand to study interactions between the ligand and different metals. At the same time, the calculation of binding energy, the analysis of characteristics for the complex structure and the distribution of frontier molecular orbital were also completed. On the basis of Marcus theory, the reorganization energy, matrix element and charge transport rate constant were calculated. The results show that the order of the charge transfer rates is Fe^(3+)>Cu^(2+)>Al^(3+) for different metal complexes, and are in good agreement with the experimental ones.
基金Project supported by the National Natural Science Foundation of China (No. 20171010).
文摘The oxidation of Na4Fe(CN)6 complex by S2O8 2- anion was found to follow an outer-sphere electron transfer mechanism. We firstly carried out the reaction at pH=1. The specific rate constants of the reaction, kox, are (8.1± 0.07)×10-2 and (4.3±0.1)×10-2 mol-1?L?s-1 at μ=1.0 mol?L-1 NaClO4, T=298 K for pH=1 (0.1 mol?L-1 HClO4) and 8, respectively. The activation parameters, obtained by measuring the rate constants of oxidation 283—303 K, were ?H≠=(69.0±5.6) kJ?mol-1, ?S≠=(-0.34±0.041)×102 J?mol-1?K-1 at pH=1 and ?H≠= (41.3±5.5) kJ?mol-1, ?S≠=(-1.27±0.33)×102 J?mol-1?K-1 at pH=8, respectively. The cyclic voltammetry of Fe(CN)36 -/4- shows that the oxidation is a one-electron reversible redox process with E1/2 values of 0.55 and 0.46 V vs. normal hydrogen electrode at μ=1.0 mol?L-1 LiClO4, for pH=1 and pH=8 (Tris), respectively. The kinetic results were discussed on the basis of Marcus theory.
基金Project supported by the National Natural Science Foundation of China (Grant No. 29572047)
文摘Electron transfer reactions take place readily between 2, 2, 6, 6-tetramethylpiperidine oxoammonium ions (la,lb) and phenothiazines (2a—2g), giving corresponding nitroxides (3a,3b) and phenothiazine radical cations (4a—4g). The rate constants for the electron self-exchange reactions between1 and3, as well as between2 and4, are determined by EPR and1HNMR line-broadening effect in acetonitrile. By application of the Marcus theory, the kinetics of the cross exchange reactions between1 and2 is studied.
文摘The fluorescence of gramicidin A(GA) in lipid bilayer may be quenched by Hypocre-Ilin B. When the phospholipids undergo a phase transition from gel to liquid crystalline phase, the reaction rate decreases unusually. This phenomenon has been analyzed by Marcus’ pho-toinduced electron theory, and an electron transfer inverted region hypothesis is proposed,
