Traditional ligand-field theory has to be improved by taking into account both 'pure electronic' contribution and electron-phonon interaction one (including lattice-vibrational relaxation energy). By means of ...Traditional ligand-field theory has to be improved by taking into account both 'pure electronic' contribution and electron-phonon interaction one (including lattice-vibrational relaxation energy). By means of improved ligand-field theory, R1, R2, R'3, R'2, and R'1 lines, U band, ground-state zero-field-splitting (GSZFS), and ground-state g factors of ruby and/or GSGG: Cr3+ as well as thermal shifts of GSZFS, R1 line and R2 line of ruby have been calculated.The results are in very good agreement with the experimental data. Moreover, it is found that the value of cubic-field parameter given by traditional ligand-field theory is inappropriately large. For thermal shifts of GSZFS, R1 line and R2 line of ruby, several conclusions have also been obtained.展开更多
Traditional ligand-field theory has to be improved by taking into account both pure electronic contribution and electron-phonon interaction one （including lattice-vibrational relaxation energy）. By means of improved...Traditional ligand-field theory has to be improved by taking into account both pure electronic contribution and electron-phonon interaction one （including lattice-vibrational relaxation energy）. By means of improved ligand-field theory, the R-line, t^3 2^2 T1 lines, t^2 2（^3 T1）e^4 T2, and t^2 2（^3T1）e^4T1 bands, ground-state g factor, four strain-induced level- splittings, and R-line thermal shift of MgO：Cr^3＋ have been calculated. The results are in very good agreement with the experimental data. It is found that for MgO：Cr^3＋, the contributions due to electron-phonon interaction （EPI） come from the first-order term. In thermal shift of R-line of MgO：Cr^3＋, the temperature-dependent contribution due to EPI is dominant.展开更多
Protecting clusters from coalescing by ligands has been universally adopted in the chemical synthesis of atomically precise clusters.Apart from the stabilization role,the effect of ligands on the electronic properties...Protecting clusters from coalescing by ligands has been universally adopted in the chemical synthesis of atomically precise clusters.Apart from the stabilization role,the effect of ligands on the electronic properties of cluster cores in constructing superatoms,however,has not been well understood.In this letter,a comprehensive theoretical study about the effect of an organic ligand,methylated N-heterocyclic carbene(C_(5)N_(2)H_(8)),on the geometrical and electronic properties of the aluminum-based clusters XAl_(12)(X=Al,C and P)featuring different valence electron shells was conducted by utilizing the density functional theory(DFT)calculations.It was observed that the ligand can dramatically alter the electronic properties of these aluminum-based clusters while maintaining their structural stability.More intriguingly,different from classical superatom design strategies,the proposed ligation strategy was evidenced to possess the capability of remarkably reducing the ionization potentials(IP)of these clusters forming the ligated superalkalis,which is regardless of their shell occupancy.The charge transfer complex formed during the ligation process,which regulates the electronic spectrum through the electrostatic Coulomb potential,was suggested to be responsible for such an IP drop.The ligation strategy highlighted here may provide promising opportunities in realizing the superatom synthesis in the liquid phase.展开更多
With the values of parameters obtained from improved ligand-field theory,by taking into account all theirreducible representations and their components in EPI as well as all the levels and the admixtures of basic wave...With the values of parameters obtained from improved ligand-field theory,by taking into account all theirreducible representations and their components in EPI as well as all the levels and the admixtures of basic wavefunc-tions within d^3 electronic configuration,the R-line thermal broadenings(TB)of both MgO:Cr^(3+)and MgO:V^(2+)havemicroscopic-theoretically been calculated.The results are in very good agreement with the experimental data.It is foundthat the R-line TB of MgO:Cr^(3+)or MgO:V^(2+)comes from the first-order term of EPI.The elastic Raman scattering ofacoustic phonons plays a dominant role in R-line TB of MgO:Cr^(3+)or MgO:V^(2+).展开更多
By means of an improved ligand-field theory, the ＂pure electronic＂ PS and the PS due to EPI of R line of MgO： V^2＋ have been calculated, respectively. The calculated results are in very good agreement with the exp...By means of an improved ligand-field theory, the ＂pure electronic＂ PS and the PS due to EPI of R line of MgO： V^2＋ have been calculated, respectively. The calculated results are in very good agreement with the experimental data. The behaviors of the pure electronic PS of R line of MgO：V^2＋ and the PS of its R line due to EPI are different. It is the combined effect of them that gives rise to the total PS of R line, which has satisfactorily explained the experimental results. The mixing-degree of ｜t2^2（^3T1）e^4T2〉 and ｜t2^3 ^2E〉 in the wavefunetion of R level and its variation with pressure have been calculated and analyzed. The comparison between the feature of R-line PS of MgO：V^2＋ and that of MgO：Cr^3＋ has been made.展开更多
The electron paramagnetic spectra of trigonal Mn^(2+) centers in[Co(H_(2)O)_(6)]SiF6,[Co(H_(2)O)_(6)]SnF6,and[Co(H_(2)O)_(6)]PtCl6 crystals were studied on the basis of the complete energy matrices for a d5 configurat...The electron paramagnetic spectra of trigonal Mn^(2+) centers in[Co(H_(2)O)_(6)]SiF6,[Co(H_(2)O)_(6)]SnF6,and[Co(H_(2)O)_(6)]PtCl6 crystals were studied on the basis of the complete energy matrices for a d5 configuration ion in a trigonal ligand field.When Mn^(2+) is doped in the[Co(H_(2)O)_(6)]SiF6,[Co(H_(2)O)_(6)]SnF6,and[Co(H_(2)O)_(6)]PtCl6 crystals crystals,there is a similar local distortion.The experimental results show that the local lattice structure around a trigonal Mn^(2+) center has an elongation distortion along the crystalline C3 axis.From the EPR calculation,the local lattice structure parameters R=2.278A,θ=52.6406? for[Co(H_(2)O)_(6)]SiF6,R=2.280,θ=52.4936° for[Co(H_(2)O)_(6)]SnF6 and R=2.244A,θ=53.0616? for[Co(H_(2)O)_(6)]PtCl6 were determined.展开更多
The electron paramagnetic resonance（EPR） spectra of trigonal Mn^（2＋） centers in Zn（ClO4）2·6（H2O） and Mg（ClO4）2·6（H2O） crystals were studied on the basis of the complete energy matrices for a d^5...The electron paramagnetic resonance（EPR） spectra of trigonal Mn^（2＋） centers in Zn（ClO4）2·6（H2O） and Mg（ClO4）2·6（H2O） crystals were studied on the basis of the complete energy matrices for a d^5 configuration ion in a trigonal ligand field. It was demonstrated that the local lattice structure around a trigonal Mn^（2＋） center has an compressed distortion along the crystalline c3 axis, and when Mn^（2＋） is doped in the Zn（ClO4）2·6（H2O） and Mg（ClO4）2·6（H2O） crystals, there is a similar local distortion. From the EPR calculation, the local lattice structure parameters R=2.183 2 ？, for Zn（ClO4）2·6（H2O）, R=2.130 2 ？, for Mg（ClO4）2·6（H2O） have been determined.展开更多
According to a uniform and simple method of calculating spin-lattice coupling coefficients and the pert1rbation formulas of gi factors and hyperfine structure constants Ai based on the cluster approach for 3d7 ions in...According to a uniform and simple method of calculating spin-lattice coupling coefficients and the pert1rbation formulas of gi factors and hyperfine structure constants Ai based on the cluster approach for 3d7 ions in cubic,tetragonal and trigonal octahedral crystal fields, the spin-lattice coupling coefficients Fij (F11, Fl2, F44), Zij (Z11, Z12,Z44) and also g factor and hyperfine constant A for MgO:Co2+ are calculated by using the parameters obtained from the optical spectra without adjustable parameters. The calculated results show good agreement with the observed values.The difiiculty in explaining the coeficients Fij and Zij is therefore removed.展开更多
Traditional ligand-field theory has to be improved by taking into account both pure electronic contribution and electron-phonon interaction one （including lattice-vibrational relaxation energy）. By means of improved...Traditional ligand-field theory has to be improved by taking into account both pure electronic contribution and electron-phonon interaction one （including lattice-vibrational relaxation energy）. By means of improved ligand-field theory, the R line, t^322T1 and t^322T2 lines, t^22（^3T1）e^4T2, t^22（^3T1）e^4T1 and t2e^2（^4A2）4T1 bands, g factors of t^32 ^4A2 and t32E, four strain-induced level-splittings and R-line thermal shift of MgO：V^2＋ have been calculated. The results are in very good agreement with the experimental data. It is found that for MgO：V^2＋, the contributions due to electronphonon interaction （EPI） come from the first-order term; the contributions from the second-order and higher terms are insignificant. In thermal shift of R line of MgO：V^2＋, the temperature-dependent contribution due to EPI is dominant. The results obtained in this work may be used in theoretical calculations of other effects of EPI.展开更多
The electron paramagnetic resonance (EPR) parameters (zero-Geld splitting Dand g factors g_‖, g_⊥) of Cr~(4+) ions in Ca_2 GeO_4 crystals have been calculated from thecomplete high-order perturbation formulas of EPR...The electron paramagnetic resonance (EPR) parameters (zero-Geld splitting Dand g factors g_‖, g_⊥) of Cr~(4+) ions in Ca_2 GeO_4 crystals have been calculated from thecomplete high-order perturbation formulas of EPR parameters for a 3d~2 ion in trigonal MX_4clusters. In these formulas, in addition to the contributions to EPR parameters from the widely usedcrystal-field (CF) mechanism, the contributions from the charge-transfer (CT) mechanism (which areoften neglected) are included. From the calculations, it is found that for the high valence state3d~n ions in crystals, the reasonable explanation of EPR parameters (in particular, the g factors)should take both the CF and CT mechanisms into account.展开更多
The EPR 9 factors for cubic, tetragonal and orthorhombic Fe^＋ centers in alkali halides MX （M= Li, Na; X = F, CI） are calculated from second-order perturbation formulas of g factors based on cluster approach for 3...The EPR 9 factors for cubic, tetragonal and orthorhombic Fe^＋ centers in alkali halides MX （M= Li, Na; X = F, CI） are calculated from second-order perturbation formulas of g factors based on cluster approach for 3d^7 ions in three symmetries. From calculations, the g factors of these Fe^＋ centers in MX crystals are reasonably explained and the defect structural data for the tetragonal and orthorhombic Fe^＋ centers are estimated. The results are discussed.展开更多
By means of improved ligand-field theory, the ＂pure electronic＂ pressure-induced shift （PS） and the PS due to electron-phonon interaction （EPI） of R-line of MgO：Cr^3＋ have been calculated, respectively. The ca...By means of improved ligand-field theory, the ＂pure electronic＂ pressure-induced shift （PS） and the PS due to electron-phonon interaction （EPI） of R-line of MgO：Cr^3＋ have been calculated, respectively. The calculated results are in very good agreement with the experimental data. The behaviors of the pure electronic PS of R-line of MgO：Cr^3＋ and the PS of its R-line due to EPI are different. It is the combined effect of them that gives rise to the total PS of R-line, which has satisfactorily explained the experimental results. The comparison between the feature of R-line PS of MgO：Cr^3＋ and that of R1-line PS of ruby has been made.展开更多
By extending the usual DV-X_α calculation and applying Bird's ligand-field theory, wepresent a theoretical method for calculating d-d ligand-field spectra of transition-metal com-plexes. Comparison between the ca...By extending the usual DV-X_α calculation and applying Bird's ligand-field theory, wepresent a theoretical method for calculating d-d ligand-field spectra of transition-metal com-plexes. Comparison between the calculated d-d ligand-field spectrum and the experimental (orother theoretical) results of cluster (CrF_6)^(3-) shows that this method is convenient and ef-fective.展开更多
This paper presents the complete energy matrix of the 3d2system containing the electron-electron interaction, the ligand-fieldinteraction, the spin-orbit coupling interaction, and the Zeeman interaction, in which the ...This paper presents the complete energy matrix of the 3d2system containing the electron-electron interaction, the ligand-fieldinteraction, the spin-orbit coupling interaction, and the Zeeman interaction, in which the optical spectra and g-factor of V3+andTi2+ions in the series of tetrahedral AIIBVI(AII=Zn, Cd, BVI=S, Se, Te) semiconductor materials are determined. In the inves-tigation of the optical and magnetic properties of these transition-metal ions in the tetrahedral coordination complexes, wecompared the data obtained from the transition-metal ions in the tetrahedral coordination complexes with those obtained fromthe corresponding ions in the octahedral ones, and found that the tetrahedral complexes have weaker crystal-field strength, in-verse energy level ordering and stronger covalence effect.展开更多
Superatoms are considered as promising building blocks for customizing superatomic molecules and cluster-assembly nanomaterials due to their tunable electronic structures and functionalities.Electron counting rules,wh...Superatoms are considered as promising building blocks for customizing superatomic molecules and cluster-assembly nanomaterials due to their tunable electronic structures and functionalities.Electron counting rules,which mainly adjust the shell-filling of clusters,are classical strategies in designing superatoms.Here,by employing the density functional theory(DFT)calculations,we proved that the 1,4-phenylene diisocyanide(CNC_(6)H_(4)NC)ligand could dramatically reduce the adiabatic ionization potentials(AlPs)of the aluminum-based clusters,which have 39,40,and 41 valence electrons,respectively,to give rise to superalkali species without changing their shell-filling.Moreover,the rigid structure of the ligand can be used as a bridge firmly linking the same or different aluminum-based clusters to form superatomic molecules and nanowires.In particular,the bridging process was observed to enhance their nonlinear optical(NLO)responses,which can be further promoted by the oriented external electric field(OEEF).Also,the stable cluster-assembly XAl_(12)(CNC_(6)H_(4)NC)(X=Al,C,and P)nanowires were constructed,which exhibit strong absorption in the visible light region.These findings not only suggest an effective ligand-field strategy in superatom design but also unveil the geometrical and electronic evolution from the CNC_(6)H_(4)NC-based superatoms to superatomic molecules and nanomaterials.展开更多
文摘Traditional ligand-field theory has to be improved by taking into account both 'pure electronic' contribution and electron-phonon interaction one (including lattice-vibrational relaxation energy). By means of improved ligand-field theory, R1, R2, R'3, R'2, and R'1 lines, U band, ground-state zero-field-splitting (GSZFS), and ground-state g factors of ruby and/or GSGG: Cr3+ as well as thermal shifts of GSZFS, R1 line and R2 line of ruby have been calculated.The results are in very good agreement with the experimental data. Moreover, it is found that the value of cubic-field parameter given by traditional ligand-field theory is inappropriately large. For thermal shifts of GSZFS, R1 line and R2 line of ruby, several conclusions have also been obtained.
文摘Traditional ligand-field theory has to be improved by taking into account both pure electronic contribution and electron-phonon interaction one （including lattice-vibrational relaxation energy）. By means of improved ligand-field theory, the R-line, t^3 2^2 T1 lines, t^2 2（^3 T1）e^4 T2, and t^2 2（^3T1）e^4T1 bands, ground-state g factor, four strain-induced level- splittings, and R-line thermal shift of MgO：Cr^3＋ have been calculated. The results are in very good agreement with the experimental data. It is found that for MgO：Cr^3＋, the contributions due to electron-phonon interaction （EPI） come from the first-order term. In thermal shift of R-line of MgO：Cr^3＋, the temperature-dependent contribution due to EPI is dominant.
基金supported by the Innovation Project of Jinan Science and Technology Bureau(No.2021GXRC032)the Taishan Scholars Project of Shandong Province(No.ts201712011)+4 种基金the National Natural Science Foundation of China(NSFC,Nos.92161101,21603119)the Natural Science Foundation of Shandong Province(No.ZR2020ZD35)the Shandong University Multidisciplinary Research and Innovation Team of Young Scholars(No.2020QNQT015)the Young Scholars Program of Shandong University(YSPSDU,No.2018WLJH48)the Fundamental Research Funds of Shandong University(No.2017TB003).
文摘Protecting clusters from coalescing by ligands has been universally adopted in the chemical synthesis of atomically precise clusters.Apart from the stabilization role,the effect of ligands on the electronic properties of cluster cores in constructing superatoms,however,has not been well understood.In this letter,a comprehensive theoretical study about the effect of an organic ligand,methylated N-heterocyclic carbene(C_(5)N_(2)H_(8)),on the geometrical and electronic properties of the aluminum-based clusters XAl_(12)(X=Al,C and P)featuring different valence electron shells was conducted by utilizing the density functional theory(DFT)calculations.It was observed that the ligand can dramatically alter the electronic properties of these aluminum-based clusters while maintaining their structural stability.More intriguingly,different from classical superatom design strategies,the proposed ligation strategy was evidenced to possess the capability of remarkably reducing the ionization potentials(IP)of these clusters forming the ligated superalkalis,which is regardless of their shell occupancy.The charge transfer complex formed during the ligation process,which regulates the electronic spectrum through the electrostatic Coulomb potential,was suggested to be responsible for such an IP drop.The ligation strategy highlighted here may provide promising opportunities in realizing the superatom synthesis in the liquid phase.
基金supported partially by National Natural Science Foundation of China under Grant No.40841012
文摘With the values of parameters obtained from improved ligand-field theory,by taking into account all theirreducible representations and their components in EPI as well as all the levels and the admixtures of basic wavefunc-tions within d^3 electronic configuration,the R-line thermal broadenings(TB)of both MgO:Cr^(3+)and MgO:V^(2+)havemicroscopic-theoretically been calculated.The results are in very good agreement with the experimental data.It is foundthat the R-line TB of MgO:Cr^(3+)or MgO:V^(2+)comes from the first-order term of EPI.The elastic Raman scattering ofacoustic phonons plays a dominant role in R-line TB of MgO:Cr^(3+)or MgO:V^(2+).
文摘By means of an improved ligand-field theory, the ＂pure electronic＂ PS and the PS due to EPI of R line of MgO： V^2＋ have been calculated, respectively. The calculated results are in very good agreement with the experimental data. The behaviors of the pure electronic PS of R line of MgO：V^2＋ and the PS of its R line due to EPI are different. It is the combined effect of them that gives rise to the total PS of R line, which has satisfactorily explained the experimental results. The mixing-degree of ｜t2^2（^3T1）e^4T2〉 and ｜t2^3 ^2E〉 in the wavefunetion of R level and its variation with pressure have been calculated and analyzed. The comparison between the feature of R-line PS of MgO：V^2＋ and that of MgO：Cr^3＋ has been made.
基金Funded by the National Natural Science Foundation of China (Nos. 11804285 and 61601384)。
文摘The electron paramagnetic spectra of trigonal Mn^(2+) centers in[Co(H_(2)O)_(6)]SiF6,[Co(H_(2)O)_(6)]SnF6,and[Co(H_(2)O)_(6)]PtCl6 crystals were studied on the basis of the complete energy matrices for a d5 configuration ion in a trigonal ligand field.When Mn^(2+) is doped in the[Co(H_(2)O)_(6)]SiF6,[Co(H_(2)O)_(6)]SnF6,and[Co(H_(2)O)_(6)]PtCl6 crystals crystals,there is a similar local distortion.The experimental results show that the local lattice structure around a trigonal Mn^(2+) center has an elongation distortion along the crystalline C3 axis.From the EPR calculation,the local lattice structure parameters R=2.278A,θ=52.6406? for[Co(H_(2)O)_(6)]SiF6,R=2.280,θ=52.4936° for[Co(H_(2)O)_(6)]SnF6 and R=2.244A,θ=53.0616? for[Co(H_(2)O)_(6)]PtCl6 were determined.
基金Funded in Part by the National Natural Science Foundation of China(No.61601384)
文摘The electron paramagnetic resonance（EPR） spectra of trigonal Mn^（2＋） centers in Zn（ClO4）2·6（H2O） and Mg（ClO4）2·6（H2O） crystals were studied on the basis of the complete energy matrices for a d^5 configuration ion in a trigonal ligand field. It was demonstrated that the local lattice structure around a trigonal Mn^（2＋） center has an compressed distortion along the crystalline c3 axis, and when Mn^（2＋） is doped in the Zn（ClO4）2·6（H2O） and Mg（ClO4）2·6（H2O） crystals, there is a similar local distortion. From the EPR calculation, the local lattice structure parameters R=2.183 2 ？, for Zn（ClO4）2·6（H2O）, R=2.130 2 ？, for Mg（ClO4）2·6（H2O） have been determined.
文摘According to a uniform and simple method of calculating spin-lattice coupling coefficients and the pert1rbation formulas of gi factors and hyperfine structure constants Ai based on the cluster approach for 3d7 ions in cubic,tetragonal and trigonal octahedral crystal fields, the spin-lattice coupling coefficients Fij (F11, Fl2, F44), Zij (Z11, Z12,Z44) and also g factor and hyperfine constant A for MgO:Co2+ are calculated by using the parameters obtained from the optical spectra without adjustable parameters. The calculated results show good agreement with the observed values.The difiiculty in explaining the coeficients Fij and Zij is therefore removed.
文摘Traditional ligand-field theory has to be improved by taking into account both pure electronic contribution and electron-phonon interaction one （including lattice-vibrational relaxation energy）. By means of improved ligand-field theory, the R line, t^322T1 and t^322T2 lines, t^22（^3T1）e^4T2, t^22（^3T1）e^4T1 and t2e^2（^4A2）4T1 bands, g factors of t^32 ^4A2 and t32E, four strain-induced level-splittings and R-line thermal shift of MgO：V^2＋ have been calculated. The results are in very good agreement with the experimental data. It is found that for MgO：V^2＋, the contributions due to electronphonon interaction （EPI） come from the first-order term; the contributions from the second-order and higher terms are insignificant. In thermal shift of R line of MgO：V^2＋, the temperature-dependent contribution due to EPI is dominant. The results obtained in this work may be used in theoretical calculations of other effects of EPI.
文摘The electron paramagnetic resonance (EPR) parameters (zero-Geld splitting Dand g factors g_‖, g_⊥) of Cr~(4+) ions in Ca_2 GeO_4 crystals have been calculated from thecomplete high-order perturbation formulas of EPR parameters for a 3d~2 ion in trigonal MX_4clusters. In these formulas, in addition to the contributions to EPR parameters from the widely usedcrystal-field (CF) mechanism, the contributions from the charge-transfer (CT) mechanism (which areoften neglected) are included. From the calculations, it is found that for the high valence state3d~n ions in crystals, the reasonable explanation of EPR parameters (in particular, the g factors)should take both the CF and CT mechanisms into account.
基金The project supported by National Natural Science Foundation of China under Grant No. 10274054
文摘The EPR 9 factors for cubic, tetragonal and orthorhombic Fe^＋ centers in alkali halides MX （M= Li, Na; X = F, CI） are calculated from second-order perturbation formulas of g factors based on cluster approach for 3d^7 ions in three symmetries. From calculations, the g factors of these Fe^＋ centers in MX crystals are reasonably explained and the defect structural data for the tetragonal and orthorhombic Fe^＋ centers are estimated. The results are discussed.
文摘By means of improved ligand-field theory, the ＂pure electronic＂ pressure-induced shift （PS） and the PS due to electron-phonon interaction （EPI） of R-line of MgO：Cr^3＋ have been calculated, respectively. The calculated results are in very good agreement with the experimental data. The behaviors of the pure electronic PS of R-line of MgO：Cr^3＋ and the PS of its R-line due to EPI are different. It is the combined effect of them that gives rise to the total PS of R-line, which has satisfactorily explained the experimental results. The comparison between the feature of R-line PS of MgO：Cr^3＋ and that of R1-line PS of ruby has been made.
基金Project supported by the National Natural Science Foundation of China.
文摘By extending the usual DV-X_α calculation and applying Bird's ligand-field theory, wepresent a theoretical method for calculating d-d ligand-field spectra of transition-metal com-plexes. Comparison between the calculated d-d ligand-field spectrum and the experimental (orother theoretical) results of cluster (CrF_6)^(3-) shows that this method is convenient and ef-fective.
基金supported by the National Natural Science Foundation of China (Grant Nos. 10974138 and 10774103)
文摘This paper presents the complete energy matrix of the 3d2system containing the electron-electron interaction, the ligand-fieldinteraction, the spin-orbit coupling interaction, and the Zeeman interaction, in which the optical spectra and g-factor of V3+andTi2+ions in the series of tetrahedral AIIBVI(AII=Zn, Cd, BVI=S, Se, Te) semiconductor materials are determined. In the inves-tigation of the optical and magnetic properties of these transition-metal ions in the tetrahedral coordination complexes, wecompared the data obtained from the transition-metal ions in the tetrahedral coordination complexes with those obtained fromthe corresponding ions in the octahedral ones, and found that the tetrahedral complexes have weaker crystal-field strength, in-verse energy level ordering and stronger covalence effect.
基金supported by the Taishan Scholars Project of Shandong Province(No.ts201712011)the National Natural Science Foundation of China(NSFC)(Nos.21603119 and 21705093)+3 种基金the Natural Science Foundation of Jiangsu Province(No.BK20170396)the Natural Science Foundation of Shandong Province(No.ZR2020ZD35)the Young Scholars Program of Shandong University(YSPSDU)(No.2018WLJH48)the Qilu Youth Scholar Funding of Shandong University.
文摘Superatoms are considered as promising building blocks for customizing superatomic molecules and cluster-assembly nanomaterials due to their tunable electronic structures and functionalities.Electron counting rules,which mainly adjust the shell-filling of clusters,are classical strategies in designing superatoms.Here,by employing the density functional theory(DFT)calculations,we proved that the 1,4-phenylene diisocyanide(CNC_(6)H_(4)NC)ligand could dramatically reduce the adiabatic ionization potentials(AlPs)of the aluminum-based clusters,which have 39,40,and 41 valence electrons,respectively,to give rise to superalkali species without changing their shell-filling.Moreover,the rigid structure of the ligand can be used as a bridge firmly linking the same or different aluminum-based clusters to form superatomic molecules and nanowires.In particular,the bridging process was observed to enhance their nonlinear optical(NLO)responses,which can be further promoted by the oriented external electric field(OEEF).Also,the stable cluster-assembly XAl_(12)(CNC_(6)H_(4)NC)(X=Al,C,and P)nanowires were constructed,which exhibit strong absorption in the visible light region.These findings not only suggest an effective ligand-field strategy in superatom design but also unveil the geometrical and electronic evolution from the CNC_(6)H_(4)NC-based superatoms to superatomic molecules and nanomaterials.
