In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond d...In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.展开更多
The characteristics of water-soluble ions in size-resolved particulate matter were investigated usingion chromatography at Shangdianzi, a regional background station of Beijing, Tianjin, and Hebei. Seasonal total conc...The characteristics of water-soluble ions in size-resolved particulate matter were investigated usingion chromatography at Shangdianzi, a regional background station of Beijing, Tianjin, and Hebei. Seasonal total concentrations of ions (Na+, Mg2+, IC, Ca2+, NH+4, Cl-, SO2-4 and NO-3) were 75.5 ± 52.9 μg/m3 in spring, 26.5 ± 12.3 Bg/m3 in summer, 22.7 ± 20.4 μg/m3 in autumn, and 31.1 ± 23.9 μg/m3 in winter, respectively. The secondary ions (NO3, SO2-4 and NH+4), mainly associated with fine particles, accounted for 84.2% in spring, 82.1% in summer, 81.5% in autumn and 76.3% in winter of all ions. Strong correlations were found between NH+4 and SO2-4 (r = 0.95, p 〈 0.01) as well as NH+4 and NO-3 (r = 0.90, p 〈 0.01) in fine particles; while in coarse particles, correlations between Mg2+ and NO-3 (r = 0.80, p 〈 0.01), and Ca2+ and NO2+ (r = 0.85, p 〈 0.01) were found. The concentrations of Na+, IC, Mg2+, Ca2+, NH+4, Cl-, NO3, and SC2-4 were 2.02, 0.81, 0.36, 1.65, 9.58, 4.01, 18.9, and 18.4 μg/m3 in particulate matter from southeast-derived air masses, which were typically 1.58-3.37 times higher than in northwest trajectories. Thus, concentrations of water-soluble ions at this background station were heavily influenced by regional transport of serious pollution derived from biomass burning, coal combustion, industrial and vehicle exhaust emissions from Beijing, Tianjin, and Hebei.展开更多
Based on the completely parametric crystal-field model, the energy level parameters, including free-ion parameters and crystal-field parameters, obtained by fitting the experimental energy level data sets of Ln^(3+...Based on the completely parametric crystal-field model, the energy level parameters, including free-ion parameters and crystal-field parameters, obtained by fitting the experimental energy level data sets of Ln^(3+) in LiYF_4 were systematically analyzed. The results revealed that the regular variation trends of the major parameters at relatively low site symmetry still existed. The g factors of ground states were calculated using the parameters obtained from least-squares fitting. The results for Ce^(3+), Nd^(3+), Sm^(3+), Dy^(3+) and Yb^(3+) were in good agreement with experiment, while those of Er^(3+) deviated from experiment dramatically. Further study showed that the g factors depended strongly on B_4~6, and a slightly different B_4~6 value of -580cm^(-1) led to g factors agreeing well with the experimental values.展开更多
文摘In this paper,the influence of crystal-field on the Luminescence properties of Eu^(2+) in complex oxides are studied theoretically by using purely electrostatic model,the dependence of the 4f^65d levels on Eu-O bond distance is given.Quantum chemistry calculation shows that the splitting extent of 4f^65d energy band in cubic or in octahedral fields will be inversely proportional to R^5,where R is the distance of Eu^(2+) to oxygen ligand.The value of R affects slightly the location of the centre of 4f^65d energy band.According to the exper- imental spectrum data,we have discussed the influence of the host chemical composition,the replaced sites of Eu^(2+) and degree of covalency of Eu-O bond on luminescence properties of Eu^(2+).Some regularity of fluorescence spectrum was observed. In alkali-alkaline earth-phosphates,the splitting extent of 4f^65d band (△E) becomes smaller as the Eu-O bond distance (R) increases.In Na_(3-x)(PO_4)_(1-x)(SO_4)_x and Na_(2-x)CaSi_(1-x)P_xO_4 hosts,d-d emission peak of Eu^(2+) will shift to shorter wavelength with the increase of x's value. The crystal structure data show that Eu^(2+) in K_2Mg_2(SO_4)_3 is affected more strongly by crystal-field and covalancy than in KMgF_3,so K_2Mg_2(SO_4)_3:Eu^(2+) emits blue light (E_(em)~m=400nm) and KMgF_3:Eu^(2+) produces ultraviolet fluorescence.
基金supported by the National Environmental Protection Commonweal Research Project(No.201509062 and No.201409073)the National Natural Science Foundation of China(No.41105089)+1 种基金Research Project of Environmental Development Cenre(No.DY-2016-5)State Key Laboratory of Environmental Criteria and Risk Assessment,Chinese Research Academy of Environmental Sciences(No.SKLECRA201637)
文摘The characteristics of water-soluble ions in size-resolved particulate matter were investigated usingion chromatography at Shangdianzi, a regional background station of Beijing, Tianjin, and Hebei. Seasonal total concentrations of ions (Na+, Mg2+, IC, Ca2+, NH+4, Cl-, SO2-4 and NO-3) were 75.5 ± 52.9 μg/m3 in spring, 26.5 ± 12.3 Bg/m3 in summer, 22.7 ± 20.4 μg/m3 in autumn, and 31.1 ± 23.9 μg/m3 in winter, respectively. The secondary ions (NO3, SO2-4 and NH+4), mainly associated with fine particles, accounted for 84.2% in spring, 82.1% in summer, 81.5% in autumn and 76.3% in winter of all ions. Strong correlations were found between NH+4 and SO2-4 (r = 0.95, p 〈 0.01) as well as NH+4 and NO-3 (r = 0.90, p 〈 0.01) in fine particles; while in coarse particles, correlations between Mg2+ and NO-3 (r = 0.80, p 〈 0.01), and Ca2+ and NO2+ (r = 0.85, p 〈 0.01) were found. The concentrations of Na+, IC, Mg2+, Ca2+, NH+4, Cl-, NO3, and SC2-4 were 2.02, 0.81, 0.36, 1.65, 9.58, 4.01, 18.9, and 18.4 μg/m3 in particulate matter from southeast-derived air masses, which were typically 1.58-3.37 times higher than in northwest trajectories. Thus, concentrations of water-soluble ions at this background station were heavily influenced by regional transport of serious pollution derived from biomass burning, coal combustion, industrial and vehicle exhaust emissions from Beijing, Tianjin, and Hebei.
基金Project supported by the National Key Basic Research Program of China(2013CB921800)the National Natural Science Foundation of China(11274299,11374291,11574298,11204292,11404321)the Anhui Provincial Natural Science Foundation(1308085QE75)
文摘Based on the completely parametric crystal-field model, the energy level parameters, including free-ion parameters and crystal-field parameters, obtained by fitting the experimental energy level data sets of Ln^(3+) in LiYF_4 were systematically analyzed. The results revealed that the regular variation trends of the major parameters at relatively low site symmetry still existed. The g factors of ground states were calculated using the parameters obtained from least-squares fitting. The results for Ce^(3+), Nd^(3+), Sm^(3+), Dy^(3+) and Yb^(3+) were in good agreement with experiment, while those of Er^(3+) deviated from experiment dramatically. Further study showed that the g factors depended strongly on B_4~6, and a slightly different B_4~6 value of -580cm^(-1) led to g factors agreeing well with the experimental values.