Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains un...Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains unclear.Additionally,the modulation of reactive oxygen species in Fenton-like reactions remains challenging.Herein,a novel strategy is reported for the rational design of highly loaded Co ASACs(CoN_(1)C_(2)/C_(2)N)immobilized on three-dimensional flower-like C_(2)N using an in situ-generated carbon defect method.In particular,the asymmetrically tricoordinated CoN_(1)C_(2)/C_(2)N exhibited excellent catalytic activity for sulfachloropyridazine degradation,with a turnover frequency of 36.8 min^(–1).Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration(t_(2g)^(6)e_(g)^(1))to the high-spin configuration(t_(2g)^(5)e_(g)^(2))owing to asymmetric coordination.The high-spin Co 3d orbital in CoN_(1)C_(2)/C_(2)N possessed more unpaired electrons and therefore,had a strong ability to gain electrons from the O 2p orbitals of HSO_(5)^(–),boosting d-p orbital hybridization.More importantly,the spin-electron filling in theσ^(*)orbital of high-spin Co 3d−O 2p accelerated the desorption of^(*)SO_(5)•^(−),which acted as a rate-limiting step in the reaction,thus facilitating more^(1)O_(2)generation.This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state,paving the way for advancements in environmental remediation and energy conversion applications.展开更多
Carbon nanofibers(CNFs)with high specific surface area show great potential for sodium storage as a hard carbon material.Herein,CNFs anchored with Ni nanoparticles(CNFs/Ni)were prepared through chemical vapor depositi...Carbon nanofibers(CNFs)with high specific surface area show great potential for sodium storage as a hard carbon material.Herein,CNFs anchored with Ni nanoparticles(CNFs/Ni)were prepared through chemical vapor deposition and impregnation reduction methods,in situ growing on the three-dimensional porous copper current collector(3DP-Cu).The coupling effect of high-spin state Ni nanopar-ticles leads to the increase of defect density and the expansion of lattice spacing of CNFs.Meanwhile,the 3DP-Cu ensures a high loading capacity of CNFs and short ion/electron transport channels.As an integral binder-free anode,the 3DP-Cu/CNFs/Ni exhibits excellent electrochemical performance,which demon-strates a high specific capacity with 298.5 mAh g^(-1)at 1000 mA g^(-1)after 1500 cycles,and a high power density with 200 mAh g^(-1)over 1000 cycles at 5000 mA g^(-1).Density functional theory calculation re-sults show that the high-spin state Ni regulates the electronic structure of CNFs,which significantly reduces the adsorption energy for Na^(+)(-2.7 Ev)and thus enables high-rate capability.The regulation of the electronic structure of carbon materials by high-spin state metal provides a new strategy for developing high-power carbonaceous anode materials for sodium-ion batteries.展开更多
Novel stable high spin molecules possessing three different arranged fashions are designed with - · N-N< as a spin-containing(SC) fragment, phenylene as an end group and various aromatic molecules, such as ben...Novel stable high spin molecules possessing three different arranged fashions are designed with - · N-N< as a spin-containing(SC) fragment, phenylene as an end group and various aromatic molecules, such as benzene(1), 2,6-pyridine(2), 3,5-pyridine(3), pyridazine(4), 4,6-pyrimidine(5), 2,6-pyrimidine(6), pyrazine(7) and triazine(8), as a ferromagnetic coupling(FC) unit. The effects of the different coupling units on the spin multiplicities of the ground states and their stabilities were investigated by means of AM1-CI approach. It has been found that the spin densities on the two atoms of the SC fragment are different from delocalization results in the specific stability of - · N-N<. In these molecules, the stabilities of the triplet states decrease when the distance between the atoms of central SC(-N-) increases. It is shown that the heterocycles as the coupling units have influence on the stabilities of the high-spin ground states. That the heteroatom lying in m -phenyl can improve ferromagnetic coupling, while the heteroatom lying in o -phenyl or p -phenyl is not in favor of the ferromagnetic coupling.展开更多
Novel stable high-spin molecules possessing three different arranging fashions were designed with —^＊N—S— as a spin-containing （SC） fragment, an aromatic group, such as benzene （ 1 ）, pyridine （2）, pyridazi...Novel stable high-spin molecules possessing three different arranging fashions were designed with —^＊N—S— as a spin-containing （SC） fragment, an aromatic group, such as benzene （ 1 ）, pyridine （2）, pyridazine （3） , pyrimidine （4）, pyrazine （5） or triazine （6） as end groups （EG）, and phenyl as a ferromagnetic coupling （FC） unit. The effects of different EG on the spin multiplicities of the ground states and their stabilities were investigated by means of the AM1-CI approach. All the investigated molecules corresponded to the FC and possessed high-spin ground states. The spin on the two atoms of the SC fragment was not in agreement with the delocalization results in the specific stability of —^＊N—S—. In those molecules, the stabilities of the triplet states decreased when the distance between the atoms of central SC fragments （—N—） increased. The stabilities of the triplet states of compounds 1a-n, 1b-n and 1c-n, with heterocycles as EG were higher than those of the triplet states of those compounds with phenyl as EG. Furthermore, the stahilities of the triplet states of the compounds with pyrimidine and triazine as EG were higher than those with pyridine, pyridazine or pyrasine as EG.展开更多
We investigate the rotating wave approximation applied in the high-spin quantum system driven by a linearly polarized alternating magnetic field in the presence of quadrupole interactions.The conventional way to apply...We investigate the rotating wave approximation applied in the high-spin quantum system driven by a linearly polarized alternating magnetic field in the presence of quadrupole interactions.The conventional way to apply the rotating wave approximation in a driven high-spin system is to assume the dynamics being restricted in the reduced Hilbert space.However,when the driving strength is relatively strong or the driving is off resonant,the leakage from the target resonance subspace cannot be neglected for a multi-level quantum system.We propose the correct formalism to apply the rotating wave approximation in the full Hilbert space by taking this leakage into account.By estimating the operator fidelity of the time propagator,our formalism applied in the full Hilbert space unambiguously manifests great advantages over the conventional method applied in the reduced Hilbert space.展开更多
A truncated shell model approach is applied to the description of high-spinstates for <sup>162</sup>Hf and <sup>164</sup>Hf isotopes.The backbends of the moment of inertia are repro-duced well ...A truncated shell model approach is applied to the description of high-spinstates for <sup>162</sup>Hf and <sup>164</sup>Hf isotopes.The backbends of the moment of inertia are repro-duced well by the calculation.The results show that the approach is able to investigatethe yrast states of nuclei in rare earth region.展开更多
The high-spin states of 141pro nucleus have been studied by using in-beam v-ray spectroscopy technology through the126Te（19F, 4n） reaction at a beam energy of 90 MeV. The previous level scheme has been extended with...The high-spin states of 141pro nucleus have been studied by using in-beam v-ray spectroscopy technology through the126Te（19F, 4n） reaction at a beam energy of 90 MeV. The previous level scheme has been extended with spin up to 49/2 h. Many new levels and transitions are identified. Five collective band structures are observed. Based on systematic comparison with the neighboring nuclei, two bands with strong AI = 1 M1 transitions inside the bands are proposed as the oblate bands with γ--60°, and three bands with large signature splitting have been suggested as the oblate-triaxial deformation with γ--90°. The characteristics for these bands have been discussed.展开更多
High-spin states of 156Yb have been studied via the 144Sm(16O,4n)156Yb fusion-evaporation reaction at beam energy 102 MeV. The positive-parity yrast band and negative-parity cascade have been extended up to higher-spi...High-spin states of 156Yb have been studied via the 144Sm(16O,4n)156Yb fusion-evaporation reaction at beam energy 102 MeV. The positive-parity yrast band and negative-parity cascade have been extended up to higher-spin states, respectively. The characteristics of the negative-parity sequence above the 25-state may related to the excitation from the nucleon in the Z =64, N =82 core. The E-GOS curve for the positiveparity yrast sequence in 156Yb indicate that this nucleus may undergo an evolution from quasivibrational to quasirotational structure with increasing angular momentum. The Cranked Woods-Saxon-Strutinsky calculations by means of Total-Routhian-Surface (TRS) methods has been made to understand this structure change.展开更多
Novel stable high spin molecules possessing three different arranged fashions are designed with -·N-N〈 as a spin-containing （SC） fragment, various aromatic, such as benzene （1）, pyridine （2）, pyridazine （...Novel stable high spin molecules possessing three different arranged fashions are designed with -·N-N〈 as a spin-containing （SC） fragment, various aromatic, such as benzene （1）, pyridine （2）, pyridazine （3）, pyrimidine （4）, pyrazine （5）, triazine （6） as end groups （EG） and phenyl as a ferromagnetic coupling （FC） unit. The effects of a different end groups on the spin multiplicities of the ground states and their stabilities were investigated by means of AM1-CI approach. It has been found that the spin densities on the two atoms of the SC fragment are different from delocalization resulting in the specific stability of -·N-N〈. In these molecules, the stabilities of the triplet states decrease when the distance between the atoms of central SC （-N-） increases. The orders of the stability of triplet states for 1an, 1bn, 1cn [They are isomers in which SC is connected with FC in different way （1an, N1NNN1; 1bn, N1N N1N; 1cn, NN1N1N） and six heterocycles are EG] show that the stability of triplet states with heterocycles as end groups is higher than that with phenyl as end groups, and in the order： triazine （EG） 〉 pyrimidine, pyrazine 〉 pyridine, pyridazine.展开更多
Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-1,10...Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-1,10-phenanthroline(NO2-phen) (2), 2,2'-bipyridyl(bpy) (3) and 4,4'-dimethyl-2,2'-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)2.3H2O has been studied in the 4-300 K range, giving the exchange integral J=-109 cm-1. The MT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.展开更多
The neutron-rich nuclei near doubly magic132^(Sn)have attracted considerable interest in both nuclear physics and nuclear astrophysics.For the particle-hole nuclei in this region,the low-lying and high core excitation...The neutron-rich nuclei near doubly magic132^(Sn)have attracted considerable interest in both nuclear physics and nuclear astrophysics.For the particle-hole nuclei in this region,the low-lying and high core excitations have been well described by shell model calculations using the extended pairing plus multipole-multipole force model.However,there is a significant difference between experiment and theory in the high-spin level 17+of^(132)Te.We intend to illustrate this difference through monopole interactions.For this purpose,the monopole corrections betweenπ(ν)0g_(7/2),ν1d_(5/2)andπ(ν)0h_(11/2)are investigated in^(132-134)Te,^(131-133)Sb,and^(130)Sn.Some theoretical levels are connected to the(17^(+))state of^(132)Te with the monopole correction(Mc)of Mc(νd_(5/2),νh_(11/2))and the quadruple-quadruple force between the proton and neutron,i.e.,levels 3^(-)(8^(-))in^(130)Sn,level 14^(-)in^(132)Te,and level 23/2^(-)in^(131)Sb.Their observations at lower energies can confirm the datum of level(17^(+))in^(132)Te with an illustration of monopole effects and quadruple-quadruple force.展开更多
文摘Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains unclear.Additionally,the modulation of reactive oxygen species in Fenton-like reactions remains challenging.Herein,a novel strategy is reported for the rational design of highly loaded Co ASACs(CoN_(1)C_(2)/C_(2)N)immobilized on three-dimensional flower-like C_(2)N using an in situ-generated carbon defect method.In particular,the asymmetrically tricoordinated CoN_(1)C_(2)/C_(2)N exhibited excellent catalytic activity for sulfachloropyridazine degradation,with a turnover frequency of 36.8 min^(–1).Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration(t_(2g)^(6)e_(g)^(1))to the high-spin configuration(t_(2g)^(5)e_(g)^(2))owing to asymmetric coordination.The high-spin Co 3d orbital in CoN_(1)C_(2)/C_(2)N possessed more unpaired electrons and therefore,had a strong ability to gain electrons from the O 2p orbitals of HSO_(5)^(–),boosting d-p orbital hybridization.More importantly,the spin-electron filling in theσ^(*)orbital of high-spin Co 3d−O 2p accelerated the desorption of^(*)SO_(5)•^(−),which acted as a rate-limiting step in the reaction,thus facilitating more^(1)O_(2)generation.This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state,paving the way for advancements in environmental remediation and energy conversion applications.
基金supported by the National Natural Science Foundation of China(Nos.52271011,52102291).
文摘Carbon nanofibers(CNFs)with high specific surface area show great potential for sodium storage as a hard carbon material.Herein,CNFs anchored with Ni nanoparticles(CNFs/Ni)were prepared through chemical vapor deposition and impregnation reduction methods,in situ growing on the three-dimensional porous copper current collector(3DP-Cu).The coupling effect of high-spin state Ni nanopar-ticles leads to the increase of defect density and the expansion of lattice spacing of CNFs.Meanwhile,the 3DP-Cu ensures a high loading capacity of CNFs and short ion/electron transport channels.As an integral binder-free anode,the 3DP-Cu/CNFs/Ni exhibits excellent electrochemical performance,which demon-strates a high specific capacity with 298.5 mAh g^(-1)at 1000 mA g^(-1)after 1500 cycles,and a high power density with 200 mAh g^(-1)over 1000 cycles at 5000 mA g^(-1).Density functional theory calculation re-sults show that the high-spin state Ni regulates the electronic structure of CNFs,which significantly reduces the adsorption energy for Na^(+)(-2.7 Ev)and thus enables high-rate capability.The regulation of the electronic structure of carbon materials by high-spin state metal provides a new strategy for developing high-power carbonaceous anode materials for sodium-ion batteries.
基金Supported by the National Natural Science Foundation of China( No.2 980 4 0 0 2,2 0 2 74 0 0 6 ) ,FokYingTungEducationFoundation( No.710 13) and Foundation of Northeast Normal University( No.1114 34)
文摘Novel stable high spin molecules possessing three different arranged fashions are designed with - · N-N< as a spin-containing(SC) fragment, phenylene as an end group and various aromatic molecules, such as benzene(1), 2,6-pyridine(2), 3,5-pyridine(3), pyridazine(4), 4,6-pyrimidine(5), 2,6-pyrimidine(6), pyrazine(7) and triazine(8), as a ferromagnetic coupling(FC) unit. The effects of the different coupling units on the spin multiplicities of the ground states and their stabilities were investigated by means of AM1-CI approach. It has been found that the spin densities on the two atoms of the SC fragment are different from delocalization results in the specific stability of - · N-N<. In these molecules, the stabilities of the triplet states decrease when the distance between the atoms of central SC(-N-) increases. It is shown that the heterocycles as the coupling units have influence on the stabilities of the high-spin ground states. That the heteroatom lying in m -phenyl can improve ferromagnetic coupling, while the heteroatom lying in o -phenyl or p -phenyl is not in favor of the ferromagnetic coupling.
基金Supported by the National Natural Science Foundation of Chana(Nos. 29804002, 20274006) and Tianjin Polytechnic Univer-sity Item(Nos. 029307, 029302).
文摘Novel stable high-spin molecules possessing three different arranging fashions were designed with —^＊N—S— as a spin-containing （SC） fragment, an aromatic group, such as benzene （ 1 ）, pyridine （2）, pyridazine （3） , pyrimidine （4）, pyrazine （5） or triazine （6） as end groups （EG）, and phenyl as a ferromagnetic coupling （FC） unit. The effects of different EG on the spin multiplicities of the ground states and their stabilities were investigated by means of the AM1-CI approach. All the investigated molecules corresponded to the FC and possessed high-spin ground states. The spin on the two atoms of the SC fragment was not in agreement with the delocalization results in the specific stability of —^＊N—S—. In those molecules, the stabilities of the triplet states decreased when the distance between the atoms of central SC fragments （—N—） increased. The stabilities of the triplet states of compounds 1a-n, 1b-n and 1c-n, with heterocycles as EG were higher than those of the triplet states of those compounds with phenyl as EG. Furthermore, the stahilities of the triplet states of the compounds with pyrimidine and triazine as EG were higher than those with pyridine, pyridazine or pyrasine as EG.
基金the National Key Research and Development Program of China(Grant Nos.2017YFA0304202 and 2017YFA0205700)the National Natural Science Foundation of China(Grant Nos.11875231 and 11935012)the Fundamental Research Funds for the Central Universities(Grant No.2018FZA3005).
文摘We investigate the rotating wave approximation applied in the high-spin quantum system driven by a linearly polarized alternating magnetic field in the presence of quadrupole interactions.The conventional way to apply the rotating wave approximation in a driven high-spin system is to assume the dynamics being restricted in the reduced Hilbert space.However,when the driving strength is relatively strong or the driving is off resonant,the leakage from the target resonance subspace cannot be neglected for a multi-level quantum system.We propose the correct formalism to apply the rotating wave approximation in the full Hilbert space by taking this leakage into account.By estimating the operator fidelity of the time propagator,our formalism applied in the full Hilbert space unambiguously manifests great advantages over the conventional method applied in the reduced Hilbert space.
文摘A truncated shell model approach is applied to the description of high-spinstates for <sup>162</sup>Hf and <sup>164</sup>Hf isotopes.The backbends of the moment of inertia are repro-duced well by the calculation.The results show that the approach is able to investigatethe yrast states of nuclei in rare earth region.
基金supported by National Natural Science Foundation of China (Nos. 10975082, 10775078)the Major State Basic Research Development Program of China (No. 2007CB815005)the Special Program of Higher Education Science Foundation of China (No. 20070003149)
文摘The high-spin states of 141pro nucleus have been studied by using in-beam v-ray spectroscopy technology through the126Te（19F, 4n） reaction at a beam energy of 90 MeV. The previous level scheme has been extended with spin up to 49/2 h. Many new levels and transitions are identified. Five collective band structures are observed. Based on systematic comparison with the neighboring nuclei, two bands with strong AI = 1 M1 transitions inside the bands are proposed as the oblate bands with γ--60°, and three bands with large signature splitting have been suggested as the oblate-triaxial deformation with γ--90°. The characteristics for these bands have been discussed.
基金Supported by National Natural Science Foundation of China (10405001, 10775005, 10735010, 10605001, J0730316)Chinese Major State Basic Research Development Program (2007CB815002)
文摘High-spin states of 156Yb have been studied via the 144Sm(16O,4n)156Yb fusion-evaporation reaction at beam energy 102 MeV. The positive-parity yrast band and negative-parity cascade have been extended up to higher-spin states, respectively. The characteristics of the negative-parity sequence above the 25-state may related to the excitation from the nucleon in the Z =64, N =82 core. The E-GOS curve for the positiveparity yrast sequence in 156Yb indicate that this nucleus may undergo an evolution from quasivibrational to quasirotational structure with increasing angular momentum. The Cranked Woods-Saxon-Strutinsky calculations by means of Total-Routhian-Surface (TRS) methods has been made to understand this structure change.
文摘Novel stable high spin molecules possessing three different arranged fashions are designed with -·N-N〈 as a spin-containing （SC） fragment, various aromatic, such as benzene （1）, pyridine （2）, pyridazine （3）, pyrimidine （4）, pyrazine （5）, triazine （6） as end groups （EG） and phenyl as a ferromagnetic coupling （FC） unit. The effects of a different end groups on the spin multiplicities of the ground states and their stabilities were investigated by means of AM1-CI approach. It has been found that the spin densities on the two atoms of the SC fragment are different from delocalization resulting in the specific stability of -·N-N〈. In these molecules, the stabilities of the triplet states decrease when the distance between the atoms of central SC （-N-） increases. The orders of the stability of triplet states for 1an, 1bn, 1cn [They are isomers in which SC is connected with FC in different way （1an, N1NNN1; 1bn, N1N N1N; 1cn, NN1N1N） and six heterocycles are EG] show that the stability of triplet states with heterocycles as end groups is higher than that with phenyl as end groups, and in the order： triazine （EG） 〉 pyrimidine, pyrazine 〉 pyridine, pyridazine.
基金Project supported by the National Natural Science Foundation of China and 21st Century Youth Foundation of Tianjin,China.
文摘Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-1,10-phenanthroline(NO2-phen) (2), 2,2'-bipyridyl(bpy) (3) and 4,4'-dimethyl-2,2'-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)2.3H2O has been studied in the 4-300 K range, giving the exchange integral J=-109 cm-1. The MT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.
基金Research at ZSTU and CIAE is supported by the National Natural Science Foundation of China(U2267205,12275361)Research at SJTU is supported by the China and Germany Postdoctoral Exchange Fellowship Program 2019 from the Office of China Postdoctoral Council(20191024)
文摘The neutron-rich nuclei near doubly magic132^(Sn)have attracted considerable interest in both nuclear physics and nuclear astrophysics.For the particle-hole nuclei in this region,the low-lying and high core excitations have been well described by shell model calculations using the extended pairing plus multipole-multipole force model.However,there is a significant difference between experiment and theory in the high-spin level 17+of^(132)Te.We intend to illustrate this difference through monopole interactions.For this purpose,the monopole corrections betweenπ(ν)0g_(7/2),ν1d_(5/2)andπ(ν)0h_(11/2)are investigated in^(132-134)Te,^(131-133)Sb,and^(130)Sn.Some theoretical levels are connected to the(17^(+))state of^(132)Te with the monopole correction(Mc)of Mc(νd_(5/2),νh_(11/2))and the quadruple-quadruple force between the proton and neutron,i.e.,levels 3^(-)(8^(-))in^(130)Sn,level 14^(-)in^(132)Te,and level 23/2^(-)in^(131)Sb.Their observations at lower energies can confirm the datum of level(17^(+))in^(132)Te with an illustration of monopole effects and quadruple-quadruple force.
