The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consi...The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa （discrete variational Xa） method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3＋ ion lies around the BCB （bottom of the conduction band） while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions （WFS） with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state （TS） calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3＋ is larger than that of y^3＋ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation （of the nearest-neighbor and next nearest-neighbor eight fluorines） has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure （including zero-phonon line） of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.展开更多
The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consi...The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa （discrete variational Xa） method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3＋ ion lies around the BCB （bottom of the conduction band） while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions （WFS） with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state （TS） calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3＋ is larger than that of y^3＋ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation （of the nearest-neighbor and next nearest-neighbor eight fluorines） has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure （including zero-phonon line） of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.展开更多
The title complex 1,{[CuEu（Hbidc）2（H2O）4]·H2O}n（H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Comple...The title complex 1,{[CuEu（Hbidc）2（H2O）4]·H2O}n（H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1,with a = 7.791（2）,b = 12.058（3）,c = 12.109（3）,α = 82.189（5）,β = 72.407（5）,γ = 89.184（4）°,V = 1073.7（5）3,C18H18CuEuN4O13,Mr = 713.86,Dc = 2.208 g/cm3,μ（MoKα） = 3.967 mm-1,F（000） = 700,GOOF = 0.950,Z = 2,the final R = 0.0531 and wR = 0.1068 for I 2σ（I）.Complex 1 possess a tape-like chain structure consisting of Eu2C8O4 and Cu2Eu2C18N4O4 metallic rings alternatively arranged and is the first 3d-4f heterometallic complex based on the 1H-ben-zimidazole-5,6-dicarboxylato ligand（Hbidc）.Plenty of hydrogen-bonding and π...π stacking interactions connect the 1D chains to construct a 3D supramolecular architecture.展开更多
(GdCa)(SiO)Oapatite crystals doped with different concentrations of Ce were synthesized by the Floating Zone(FZ) method, and we have evaluated the photoluminescence(PL) and radio luminescence(RL) properties. In PL, an...(GdCa)(SiO)Oapatite crystals doped with different concentrations of Ce were synthesized by the Floating Zone(FZ) method, and we have evaluated the photoluminescence(PL) and radio luminescence(RL) properties. In PL, an emission band appeared around 400 nm under excitation at 300 nm due to the5 d-4 f transitions of Ce3+. The PL decay curves were approximated by a second-order exponential decay function, and the derived decay time constants ranged around 20-25 ns and 40-480 ns. Similar emission was observed in RL, but the decay time constants were much longer than those in PL. The RL afterglow was the lowest in the 1.0% Ce-doped sample. The 1.0% and 2.0% Ce-doped samples showed a full-energy peak in the pulse height spectrum measured underAm 5.5 MeV α-ray irradiation, and the absolute scintillation light yields were estimated to be around 55 and 36 ph/5.5 MeV-a, respectively.展开更多
The RMn_(2)O_(5) manganite compounds represent one class of multiferroic family with magnetic origins,which has been receiving continuous attention in the past decade.So far,our understanding of the magnetic origins f...The RMn_(2)O_(5) manganite compounds represent one class of multiferroic family with magnetic origins,which has been receiving continuous attention in the past decade.So far,our understanding of the magnetic origins for ferroelectricity in RMn_(2)O_(5) is associated with the nearly collinear antiferromagnetic structure of Mn ions,while the exchange striction induced ionic displacements are the consequence of the spin frustration competitions.While this scenario may be applied to almost all RMn_(2)O_(5) members,its limitation is either clear:the temperature-dependent behaviors of electric polarization and its responses to external stimuli are seriously materials dependent.These inconsistences raise substantial concern with the state-of-the-art physics of ferroelectricity in RMn_(2)O_(5).In this mini-review,we present our recent experimental results on the roles of the 4f moments from R ions which are intimately coupled with the 3d moments from Mn ions.DyMn_(2)O_(5) is a golden figure for illustrating these roles.It is demonstrated that the spin structure accommodates two nearly collinear sublattices which generate respectively two ferroelectric(FE)sublattices,enabling DyMn_(2)O_(5) an emergent ferrielectric(FIE)system rarely identified in magnetically induced FEs.The evidence is presented from several aspects,including FIE-like phenomena and magnetoelectric responses,proposed structural model,and experimental check by nonmagnetic substitutions of the 3d and 4f moments.Additional perspectives regarding possible challenges in understanding the multiferroicity of RMn_(2)O_(5) as a generalized scenario are discussed.展开更多
文摘The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa （discrete variational Xa） method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3＋ ion lies around the BCB （bottom of the conduction band） while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions （WFS） with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state （TS） calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3＋ is larger than that of y^3＋ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation （of the nearest-neighbor and next nearest-neighbor eight fluorines） has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure （including zero-phonon line） of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.
文摘The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa （discrete variational Xa） method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3＋ ion lies around the BCB （bottom of the conduction band） while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions （WFS） with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state （TS） calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3＋ is larger than that of y^3＋ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation （of the nearest-neighbor and next nearest-neighbor eight fluorines） has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure （including zero-phonon line） of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.
基金Supported by the Nanjing University of Posts and Telecommunications(No.NY209032)the National Natural Science Foundation of China(No.21001065)the Major State Basic Research Development Program of China (973 Program,No.2009CB930600)
文摘The title complex 1,{[CuEu（Hbidc）2（H2O）4]·H2O}n（H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1,with a = 7.791（2）,b = 12.058（3）,c = 12.109（3）,α = 82.189（5）,β = 72.407（5）,γ = 89.184（4）°,V = 1073.7（5）3,C18H18CuEuN4O13,Mr = 713.86,Dc = 2.208 g/cm3,μ（MoKα） = 3.967 mm-1,F（000） = 700,GOOF = 0.950,Z = 2,the final R = 0.0531 and wR = 0.1068 for I 2σ（I）.Complex 1 possess a tape-like chain structure consisting of Eu2C8O4 and Cu2Eu2C18N4O4 metallic rings alternatively arranged and is the first 3d-4f heterometallic complex based on the 1H-ben-zimidazole-5,6-dicarboxylato ligand（Hbidc）.Plenty of hydrogen-bonding and π...π stacking interactions connect the 1D chains to construct a 3D supramolecular architecture.
基金Project supported by a Grant-in-Aid for Scientific Research(A) 26249147 from the Ministry of Education,Culture,Sports,Science and Technology of Japan(MEXT)JST A-step,Cooperative Research Project of Research Institute of Electronics,Shizuoka University+1 种基金Inamori FoundationKRF Foundation
文摘(GdCa)(SiO)Oapatite crystals doped with different concentrations of Ce were synthesized by the Floating Zone(FZ) method, and we have evaluated the photoluminescence(PL) and radio luminescence(RL) properties. In PL, an emission band appeared around 400 nm under excitation at 300 nm due to the5 d-4 f transitions of Ce3+. The PL decay curves were approximated by a second-order exponential decay function, and the derived decay time constants ranged around 20-25 ns and 40-480 ns. Similar emission was observed in RL, but the decay time constants were much longer than those in PL. The RL afterglow was the lowest in the 1.0% Ce-doped sample. The 1.0% and 2.0% Ce-doped samples showed a full-energy peak in the pulse height spectrum measured underAm 5.5 MeV α-ray irradiation, and the absolute scintillation light yields were estimated to be around 55 and 36 ph/5.5 MeV-a, respectively.
基金supported by the Natural Science Foundation of China(Grant Nos.11234005 and 51431006)the National 973 Projects of China(Grant No.2011CB922101).
文摘The RMn_(2)O_(5) manganite compounds represent one class of multiferroic family with magnetic origins,which has been receiving continuous attention in the past decade.So far,our understanding of the magnetic origins for ferroelectricity in RMn_(2)O_(5) is associated with the nearly collinear antiferromagnetic structure of Mn ions,while the exchange striction induced ionic displacements are the consequence of the spin frustration competitions.While this scenario may be applied to almost all RMn_(2)O_(5) members,its limitation is either clear:the temperature-dependent behaviors of electric polarization and its responses to external stimuli are seriously materials dependent.These inconsistences raise substantial concern with the state-of-the-art physics of ferroelectricity in RMn_(2)O_(5).In this mini-review,we present our recent experimental results on the roles of the 4f moments from R ions which are intimately coupled with the 3d moments from Mn ions.DyMn_(2)O_(5) is a golden figure for illustrating these roles.It is demonstrated that the spin structure accommodates two nearly collinear sublattices which generate respectively two ferroelectric(FE)sublattices,enabling DyMn_(2)O_(5) an emergent ferrielectric(FIE)system rarely identified in magnetically induced FEs.The evidence is presented from several aspects,including FIE-like phenomena and magnetoelectric responses,proposed structural model,and experimental check by nonmagnetic substitutions of the 3d and 4f moments.Additional perspectives regarding possible challenges in understanding the multiferroicity of RMn_(2)O_(5) as a generalized scenario are discussed.
