One-electron oxidation of N-4-desmethylwyosine (dYt), a derivative of rare tricyclic nucleoside wyosine with several oxidative radicals, has been studied by using pulse radiolysis. The transient spectra of the radical...One-electron oxidation of N-4-desmethylwyosine (dYt), a derivative of rare tricyclic nucleoside wyosine with several oxidative radicals, has been studied by using pulse radiolysis. The transient spectra of the radicals dYt˙+ and dYt(-H)˙ and the pK a of the radical cation were measured. The rate constants of reactions of dYt with SO 4 ˙? and CO 3 ˙? radicals have been determined and related reaction mechanisms were discussed.展开更多
Iron sites in both nitrogenase enzymes and chemical catalysts for N_(2) fixation are typically at constrained distances and angles.Herein,we report a one-electron reduction reaction realized by constrained diiron dini...Iron sites in both nitrogenase enzymes and chemical catalysts for N_(2) fixation are typically at constrained distances and angles.Herein,we report a one-electron reduction reaction realized by constrained diiron dinitrogen cores.Using the semicircular bis(β-diketiminate)ligand,a series of diiron dinitrogen complexes were synthesized,in which the N_(2) groups were allowed to bind with Fe-Ct_(N2)-Fe angles ranging from 154°to 158°(Ct_(N2)=centroid of N_(2)).One-electron reduction of complex 2a[LFe(μ-N_(2))Fe(Et_(2)O)]gave dimer product 3a[LFe(μ-N_(2))FeK]_(2)(μ-N_(2))or monomer 3b[LFe(μ-N_(2))Fe(DMAP)K].Based on superconducting quantum interference device measurements and density functional theory calculations,2a,3a,and 3b exhibited ground spin states of S=3,S=5,and S=5/2,respectively.In addition,complex 3 underwent N_(2)derivatization via a silylation pathway followed by an acidic cleavage to yield N_(2)H_(4)as the product.展开更多
Using formulae for one- and two-electron integrals of Coulomb interaction potential fk （r） = r^-k with non-integer indices k established by one of the authors with the help of complete orthonormal sets of ψ^α-expo...Using formulae for one- and two-electron integrals of Coulomb interaction potential fk （r） = r^-k with non-integer indices k established by one of the authors with the help of complete orthonormal sets of ψ^α-exponential-type orbitals （α = 1, 0,-1,-2,…）, we perform the calculations for isoelectronic series of the He atom containing nuclear charges from 2 to 10, where k = 1 - μ （-1 〈 μ 〈 0）. For this purpose we have used the double-zeta approximation, the configuration interaction and coupled-cluster methods employing the integer-n Slater-type orbitals as basis sets. It is demonstrated that the results of calculations obtained are better than the numerical Hartree-Fock values.展开更多
In this paper we propose a numerical approach to solve the relativistic Dirac equation suitable for computational calculations of one-electron systems. A variational procedure is carried out similar to the well-known ...In this paper we propose a numerical approach to solve the relativistic Dirac equation suitable for computational calculations of one-electron systems. A variational procedure is carried out similar to the well-known Hylleraas computational method. An application of the method to hydrogen isoelectronic atoms is presented, showing its consistency and high accuracy, relative to the exact analytical eigenvalues.展开更多
We study the photo-oxidation of bacteriochlorophylls （BChls） in peripheral light harvesting complexes （LH2） from rhodobacter sphaeroides by using the steady absorption and the femtosecond pump-probe measurement, t...We study the photo-oxidation of bacteriochlorophylls （BChls） in peripheral light harvesting complexes （LH2） from rhodobacter sphaeroides by using the steady absorption and the femtosecond pump-probe measurement, to realize the detailed dynamics of LH2 in the presence of photo-oxidation. The experimental results reveal that BChl-B850 radical cations may act as an additional channel to compete with the unoxidized BChl-B850 molecules for rapidly releasing the excitation energy, while the B800→B850 energy transfer rate is almost unaffected in the oxidation process.展开更多
In the molecular Ammosov–Delone–Krainov(MO-ADK) model of Tong et al. [Phys. Rev. A 66(2002)033402], the ionization rate depends on the structure parameters of the molecular orbital from which the electron is removed...In the molecular Ammosov–Delone–Krainov(MO-ADK) model of Tong et al. [Phys. Rev. A 66(2002)033402], the ionization rate depends on the structure parameters of the molecular orbital from which the electron is removed. We determine systematically and tabulate accurate structure parameters of the highest occupied molecular orbital(HOMO) for 123 gas-phase linear molecules by solving time-independent Schr¨odinger equation with B-spline functions and molecular potentials which are constructed numerically using the modified Leeuwen–Baerends(LBα)model.展开更多
Electrodynamics of the one-electron currents due to the circular orbital motion of the electron particle in the hydrogen atom has been examined. The motion is assumed to be induced by the time change of the magnetic f...Electrodynamics of the one-electron currents due to the circular orbital motion of the electron particle in the hydrogen atom has been examined. The motion is assumed to be induced by the time change of the magnetic field in the atom. A characteristic point is that the electric resistance calculated for the motion is independent of the orbit index and its size is similar to that obtained earlier experimentally for the planar free-electron-like structures considered in the integer quantum Hall effect. Other current parameters like conductivity and the relaxation time behave in a way similar to that being typical for metals. A special attention was attached to the relations between the current intensity and magnetic field. A correct reproduction of this field with the aid of the Biot-Savart law became possible when the geometrical microstructure of the electron particle has been explicitly taken into account. But the same microstructure properties do influence also the current velocity. In fact the current suitable for the Biot-Savart law should have a speed characteristic for a spinning electron particle and not that of a spinless electron circulating along the orbit of the original Bohr model.展开更多
While N-heterocyclic carbene(NHC)catalyzed electron-pair-transfer processes have been developed into an important tool for synthetically important bond formations during the past decades,the corresponding radical reac...While N-heterocyclic carbene(NHC)catalyzed electron-pair-transfer processes have been developed into an important tool for synthetically important bond formations during the past decades,the corresponding radical reactions via NHC catalysis have only received growing attention in the past six years.Taking into account the advantages NHC-catalyzed radical reactions might bring,such as creating new activation modes that were previously unobtainable,it is worthwhile to provide a conceptual understanding of this emerging area.Therefore,herein we give an overview of NHC-catalyzed radical reactions via different synthetic techniques.展开更多
The piperonal electron affinity was studied using pulse radiolysis technique. The electron transfer reaction process between piperonal and anthraquinone-2-sulfate was observed in the pH 7 phosphoric acid salt buffer. ...The piperonal electron affinity was studied using pulse radiolysis technique. The electron transfer reaction process between piperonal and anthraquinone-2-sulfate was observed in the pH 7 phosphoric acid salt buffer. The transient absorption spectra of electron transfer re-action between piperonal and anthraquinone-2-sulfate were obtained, and the initial proof of the electron transfer between electron donor and acceptor was provided directly. The one-electron reduction potential of piperonal was determined to be ?0.457 V.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.20072025)Promoted Research Programs of Chinese Academy of Sciences.
文摘One-electron oxidation of N-4-desmethylwyosine (dYt), a derivative of rare tricyclic nucleoside wyosine with several oxidative radicals, has been studied by using pulse radiolysis. The transient spectra of the radicals dYt˙+ and dYt(-H)˙ and the pK a of the radical cation were measured. The rate constants of reactions of dYt with SO 4 ˙? and CO 3 ˙? radicals have been determined and related reaction mechanisms were discussed.
基金supported by National Natural Science Foundation of China(grant nos.21988101,22201013,92161204)China Postdoctoral Science Foundation(grant no.2020M670016)Beijing Natural Science Foundation(grant no.2222008).
文摘Iron sites in both nitrogenase enzymes and chemical catalysts for N_(2) fixation are typically at constrained distances and angles.Herein,we report a one-electron reduction reaction realized by constrained diiron dinitrogen cores.Using the semicircular bis(β-diketiminate)ligand,a series of diiron dinitrogen complexes were synthesized,in which the N_(2) groups were allowed to bind with Fe-Ct_(N2)-Fe angles ranging from 154°to 158°(Ct_(N2)=centroid of N_(2)).One-electron reduction of complex 2a[LFe(μ-N_(2))Fe(Et_(2)O)]gave dimer product 3a[LFe(μ-N_(2))FeK]_(2)(μ-N_(2))or monomer 3b[LFe(μ-N_(2))Fe(DMAP)K].Based on superconducting quantum interference device measurements and density functional theory calculations,2a,3a,and 3b exhibited ground spin states of S=3,S=5,and S=5/2,respectively.In addition,complex 3 underwent N_(2)derivatization via a silylation pathway followed by an acidic cleavage to yield N_(2)H_(4)as the product.
文摘Using formulae for one- and two-electron integrals of Coulomb interaction potential fk （r） = r^-k with non-integer indices k established by one of the authors with the help of complete orthonormal sets of ψ^α-exponential-type orbitals （α = 1, 0,-1,-2,…）, we perform the calculations for isoelectronic series of the He atom containing nuclear charges from 2 to 10, where k = 1 - μ （-1 〈 μ 〈 0）. For this purpose we have used the double-zeta approximation, the configuration interaction and coupled-cluster methods employing the integer-n Slater-type orbitals as basis sets. It is demonstrated that the results of calculations obtained are better than the numerical Hartree-Fock values.
文摘In this paper we propose a numerical approach to solve the relativistic Dirac equation suitable for computational calculations of one-electron systems. A variational procedure is carried out similar to the well-known Hylleraas computational method. An application of the method to hydrogen isoelectronic atoms is presented, showing its consistency and high accuracy, relative to the exact analytical eigenvalues.
基金Supported by the National Natural Science Foundation of China under Grant Nos 10274013 and 10374020.
文摘We study the photo-oxidation of bacteriochlorophylls （BChls） in peripheral light harvesting complexes （LH2） from rhodobacter sphaeroides by using the steady absorption and the femtosecond pump-probe measurement, to realize the detailed dynamics of LH2 in the presence of photo-oxidation. The experimental results reveal that BChl-B850 radical cations may act as an additional channel to compete with the unoxidized BChl-B850 molecules for rapidly releasing the excitation energy, while the B800→B850 energy transfer rate is almost unaffected in the oxidation process.
基金Supported by National Natural Science Foundation of China under Grant Nos.11664035,11674268,11465016,11364038,11364039the Specialized Research Fund for the Doctoral Program of Higher Education of China under Grant No.20116203120001the Basic Scientific Research Foundation for Institution of Higher Learning of Gansu Province
文摘In the molecular Ammosov–Delone–Krainov(MO-ADK) model of Tong et al. [Phys. Rev. A 66(2002)033402], the ionization rate depends on the structure parameters of the molecular orbital from which the electron is removed. We determine systematically and tabulate accurate structure parameters of the highest occupied molecular orbital(HOMO) for 123 gas-phase linear molecules by solving time-independent Schr¨odinger equation with B-spline functions and molecular potentials which are constructed numerically using the modified Leeuwen–Baerends(LBα)model.
文摘Electrodynamics of the one-electron currents due to the circular orbital motion of the electron particle in the hydrogen atom has been examined. The motion is assumed to be induced by the time change of the magnetic field in the atom. A characteristic point is that the electric resistance calculated for the motion is independent of the orbit index and its size is similar to that obtained earlier experimentally for the planar free-electron-like structures considered in the integer quantum Hall effect. Other current parameters like conductivity and the relaxation time behave in a way similar to that being typical for metals. A special attention was attached to the relations between the current intensity and magnetic field. A correct reproduction of this field with the aid of the Biot-Savart law became possible when the geometrical microstructure of the electron particle has been explicitly taken into account. But the same microstructure properties do influence also the current velocity. In fact the current suitable for the Biot-Savart law should have a speed characteristic for a spinning electron particle and not that of a spinless electron circulating along the orbit of the original Bohr model.
文摘While N-heterocyclic carbene(NHC)catalyzed electron-pair-transfer processes have been developed into an important tool for synthetically important bond formations during the past decades,the corresponding radical reactions via NHC catalysis have only received growing attention in the past six years.Taking into account the advantages NHC-catalyzed radical reactions might bring,such as creating new activation modes that were previously unobtainable,it is worthwhile to provide a conceptual understanding of this emerging area.Therefore,herein we give an overview of NHC-catalyzed radical reactions via different synthetic techniques.
基金supported by the National Natural Science Foundation of China(Grant No.30100035)Natural Science Foundation of Fujian(Grant No.C0510029).
文摘The piperonal electron affinity was studied using pulse radiolysis technique. The electron transfer reaction process between piperonal and anthraquinone-2-sulfate was observed in the pH 7 phosphoric acid salt buffer. The transient absorption spectra of electron transfer re-action between piperonal and anthraquinone-2-sulfate were obtained, and the initial proof of the electron transfer between electron donor and acceptor was provided directly. The one-electron reduction potential of piperonal was determined to be ?0.457 V.
