系列二亚胺羰基Mn配合物光谱的密度泛函研究

CO₂还原始终是能源和环境领域的重要挑战。二亚胺羰基Mn配合物价格低廉,稳定性好,可调变性强,成为近年来光催化还原CO₂的热门催化剂。紫外-可见光谱和红外光谱研究有助于调控CO₂光还原催化剂性能。基于密度泛函理论(DFT)和含时密度泛函理论(TD-DFT),对系列二亚胺羰基锰配合物[Mn(bpy)(CO)₃Br],(简写为1),[Mn(phen)(CO)₃Br],(简写为2),[Mn(phen-dione)(CO)₃Br],(简写为3),[Mn(phen-dione)(CO)₃CH₃CN]⁺,(简写为4)(bpy=2,2′-bipyridine,phen=1,10-phenan-throline,phen-dione=phenanthroline-5, 6-dione)的紫外-可见光谱和红外光谱进行研究。基于TD-DFT方法,采用多种泛函,对紫外-可见光谱进行模拟。结果显示1和2主要有两个最...     

TWO PHOTONS EXCITED 4d RYDBERG STATE OF AsH3

In this paper, by using resonance enhanced (2+1) multiphoton ionization (REMPI) of AsH₃ and detecting the daughter molecular ions AsH⁺ and As⁺, a long progression discrete structure was obtained from 267 to 291 nm, which obeys the formula ν₀(cm^-1)=68875.3+504.1v′₂+5.26v′²₂. Analysis of the spectrum has revealed that it belongs to 4d Rydberg state transition. Our assignment yields the 4d Rydberg state parameters T_e′=67881.1 cm^-1, ω_e′=495.1 cm^-1 and δ=0.962. Finally the 4d Rydberg state structure of AsH₃ was discussed.     

AlH分子10个Λ-S态和26个Ω态光谱性质的理论研究

在修正了各种误差(自旋-轨道耦合效应、标量相对论效应、核价相关效应及基组截断)的基础上,本文利用内收缩的多参考组态相互作用(icMRCI)+Q方法计算了AlH分子10个Λ-S态和26个Ω态的势能曲线.利用包含自旋-轨道耦合效应的icMRCI/AV6Z~*理论计算了X¹∑_((0⁺)⁺),a³Π_0⁺,a³Π₁,a³Π₂和A¹Π₁态之间的跃迁偶极矩.计算得到的光谱常数和跃迁数据与现有的实验值符合很好.研究发现:1)A¹Π₁-X¹∑_((0⁺)⁺)(0,0),(0,1),(0,2),(1,0),(1,1),(1,2),(1,3),(1,4)和(1,5)带Q(J")支的跃迁比较强,随着J"的增大,Δv=0带的爱因斯坦A系数和振...     

非晶锂离子导体B2O3-Li2O-LiCl一Al2O3中VO2+的电子自旋共振

两种非晶锂离子导体B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃-0.1V₂O₅(x=0.05和0.15)的电子自旋共振谱研究表明:(i)ESR线型是高斯型,证实V₂O₅添加量适当;(ii)超精细结构来源于VO²⁺络离子,具有四角对称性,属C_4v群。越精细耦合张量的平行分量平均值A_//=0.0175cm^-1,垂直分量A_⊥=0.0063cm^-1。由g_//(g_⊥)求出其基态²B_2g与第一激发态²E_g的能级间距△₁=2.46×10⁴ cm^-1,基态与第二激发态²B_1g的能级间距△₂=3.03×10⁴ cm^-1;(iii)变温实验证实:Al₂O₃组分较少(x=0.05)的非晶ESR强度比x=0.15的非晶高3倍至2倍,而Al₂O₃组分越多则ESR强度随温升下降越小。     

Si中S0对、Se0对和Te0对的电子结构

利用紧束缚近似下的格林函数方法,讨论了Si中(S⁰)₂,(Se⁰)₂及(Te⁰)₂基态的能级和波函数。分析了几种不同的观点。(S⁰)₂,(Se⁰)₂及(Te⁰)₂均在禁带中引入一个对称性的A_1g能级和一个反对称性的A_2u能级,二者都是填满的。现有实验观测到的是较高的A_1g能级。从理论上指出了对称性的A_1g能级反而高于反对称性的能级的原因。而Si中(Se₂)⁺的g因子测量值和(S₂)⁺,(Se₂)⁺的ESR实验结果也支持本文的观点。 关键词：     

NaLa(MoO4)2∶Eu3+的水热调控合成与发光特性研究

采用水热法合成了不同粒径的NaLa(MoO₄)₂∶Eu³⁺微晶.通过调节乙二醇浓度和反应时间,研究了NaLa(MoO₄)₂∶Eu³⁺微晶的形貌演变过程,在水热条件下180 ℃反应16 h获得了均一梭子形NaLa(MoO₄)₂∶Eu³⁺微晶,其晶粒长度约为2.0 μm.荧光光谱分析表明,Eu³⁺取代了NaLa(MoO₄)₂中La³⁺的格位, Eu³⁺在613 nm处红光发射(⁵D₀–⁷F₂跃迁)的浓度猝灭机理是电偶极-电四极相互作用,并发生了Eu³⁺( ⁵D₁ ) + Eu³⁺(⁷F₀ )→ Eu³⁺( ⁵D₀ ) + Eu³⁺(⁷F₃) 交叉弛豫,由此导致浓度猝灭. 关键词： 钼酸盐 水热法 稀土离子 发光     

BH2和AlH2分子的结构及其解析势能函数

运用二次组态相关(QCISD)方法，分别选用6-311++G(3df,3pd)和D95(3df,3pd)基组，对BH₂和AlH₂分子的结构进行了优化计算，得到BH₂分子的稳态结构为C_2v构型，电子态为²A₁、平衡核间距R_BH=0.1187nm、键角∠HBH=128.791°、离解能D_e=3.65eV、基态振动频率ν₁(a₁)=1020.103cm^-1,ν₂(a₁)=2598.144cm^-1,ν₃(b₂)=2759.304cm^-1.AlH₂分子的稳态结构也为C_2v构型，电子态为²A₁、平衡核间距R_AlH=0.1592nm、键角∠HAlH=118.095°、离解能D_e=2.27eV、基态振动频率ν₁(a₁)=780.81cm^-1,ν₂(a₁)=1880.81cm^-1，ν₃(b₂)=1910.46cm^-1.采用多体项展式理论推导了基态BH₂和AlH₂分子的解析势能函数，其等值势能图准确再现了BH₂和AlH₂分子的结构特征及其势阱深度与位置.分析讨论势能面的静态特征时得到BH+H→BH₂反应中存在鞍点，活化能为150.204kJ/mol；AlH+H→AlH₂反应中也存在鞍点，活化能为54.8064kJ/mol. 关键词： 2')" href="#">BH₂ 2')" href="#">AlH₂ Murrell-Sorbie函数 多体项展式理论 解析势能函数     

NCO异构体结构与分析势能函数

在B3LYP/6-31+G（d）水平上,对NCO分子的各种可能结构进行几何优化,得到了NCO及其异构体分子CNO和CON基态结构都是C_∞v,电子态为X²Ⅱ,NCO分子的平衡核间距R_NC=0.1230 nm,R_CO=0.1186 nm,离解能D_e=13.40 eV,并计算出谐振频率ω₁=1293.44 cm^-1,ω₂（A′）=484.73 cm^-1,ω₂（A″）=559.72 cm^-1,ω₃=1988.41 cm^-1,Renner-Teller参数ε=-0.1429,计算值与实验值吻合较好.在此基础上,应用多体项展式理论,单体项中首次引入开关函数,三体项以NCO,CNO基态结构与性质为依据,拟合给出了NCO分子的基态分析势能函数,其等值势能图准确再现了NCO,CNO分子基态结构与特征,并与优化结果完全一致.     

电气石中离子对(Fe2+—Fe3+跃迁

本文在晶体场理论的基础上,采用Fe²⁺的自洽场解析近似3d轨道,考虑到电气石中b,c两位置的实际对称性(C_s,C₁),计算了属于3d⁶组态的Fe²⁺在该两位置的自旋允许能谱:用离子对跃迁的观点,从理论上探讨了前人尚未处理过的离子对的(Fe²⁺(g)-Fe³⁺)→(Fe²⁺(e)-Fe²⁺)跃迁;并对偏振依赖性很大的三条谱:9000cm^-1,13800cm^-1,15000cm^-1作了强度估计,较为满意地解释了电气石的近红外光谱。 关键词：     

Microstructured hydroxyl environments and Raman spectroscopy in selected basic transition-metal halides

Raman vibrational spectra of the selected basic (hydroxyl OH and deuteroxyl OD) transition-metal halides, geometrically frustrated material series α-, β-, γ-Cu₂(OH)₃Cl, α-Cu₂(OH)₃Br, β-Ni₂(OH)₃Cl, β-Co₂(OH)₃Cl, β-Co₂(OH)₃Br, γ-Cu₂(OD)₃Cl, and β-Co₂(OD)₃Cl are measured at room temperature and analysed to investigate the relationship between the microstructured OH environments and their respective Raman spectra. Among these selected samples, the last two are used to determine the OH stretching vibration region (3600 cm^-1—3300 cm^-1) and OH bending vibration region (1000 cm^-1—600 cm^-1) of OH systems in the spectra. Through the comparative analysis of the distances d(metal—O), d(O—halogen), and d(OH), the strong metal—O interaction and trimeric hydrogen bond (C_3v, C_s or C₁ symmetry) are found in every material, but both determine simultaneously an ultimate d(OH), and therefore an OH stretching vibration frequency. According to the approximately linear relationship between the OH stretching vibration frequency and d(OH), some unavailable d(OH) are guessed and some doubtful d(OH) are suggested to be corrected. In addition, it is demonstrated in brief that the OH bending vibration frequency is also of importance to check the more detailed crystal microstructure relating to the OH group.     

Eu2+在Ba2Ca(BO3)2中的发光特性及浓度猝灭

采用高温固相法,以CaCO₃ (A.R)、BaCO₃ (A.R)、H₃BO₃ (A.R)和Eu₂O₃ (99.99%)为原料制备了Ba₂Ca(BO₃)₂∶Eu²⁺绿色发光材料,测量了材料的晶体结构、发光特性及色坐标等。Ba₂Ca(BO₃)₂∶Eu²⁺材料的激发光谱覆盖200~500 nm的紫外-可见光区。在400 nm近紫外光激发下,材料的发射光谱为一主峰位于537 nm的非对称宽谱,对应于Eu²⁺的4f⁶5d¹→4f⁷特征跃迁。研究发现,随Eu²⁺掺杂浓度的增大,Ba₂Ca-(BO₃)₂∶Eu²⁺材料的发射强度呈现先增大、后减小的变化趋势,最大发射强度对应的Eu²⁺掺杂摩尔分数为2%。造成发射强度下降的原因为浓度猝灭,其机理为电偶极-电偶极相互作用。依据晶格常数及实验光谱数据,得出临界距离R_c分别为2.64 nm和2.11 nm。随Eu²⁺掺杂浓度的增大,Ba₂Ca(BO₃)₂∶Eu²⁺材料的色坐标变化微小。计算得到Ba₂Ca(BO₃)₂∶2%Eu²⁺的转换效率约为72%。     

La1.6(MoO4)3:Eu0.43+纳米晶合成及发光特性

采用燃烧法合成了La_1.6(MoO₄)₃:Eu_0.4³⁺纳米晶末,研究了其声子-掺杂-晶格相互作用和发光性质.X射线粉末衍射(XRD)分析表明,在500~900 ℃退火后,La_1.6(MoO₄)₃:Eu_0.4³⁺样品为单一晶相.对样品进行了光致发光(PL)测量,激发Mo⁶⁺-O^2-电荷迁移带,观察到Eu³⁺的系列发光,表明Mo⁶⁺-O^2-带和Eu³⁺间存在能量传递,中心波长分别在λ₁=469 nm和λ₂=426 nm处的两个one-phonon边带,相应的声子能量分别为767和1202 cm^-1,分别对应于 Mo=O 和Mo-O-Mo伸缩振动.同时,计算了两个局域模电子-声子耦合强度的黄昆因子分别为S₁=0.055和S₂=0.037,为揭示其三价离子高传导特性及其负热膨胀物理特性提供了实验基础.     

过渡族元素掺杂BaTiO3-Tb1-xDyxFe2-y层状复合材料中的磁电效应

用溶胶-凝胶法制备1.0%mol Mn,Cr,Co掺杂 BaTiO₃(BTO)粉体,在1350℃下烧结成多晶陶瓷样品.X射线衍射和差示扫描量热分析表明,室温下掺杂BaTiO₃具有四方钙钛矿结构;居里点和相变潜热随Cr,Mn,Co掺杂逐渐降低.将掺杂BaTiO₃与Tb_1-xDy_xFe_2-y(TDF)胶合制成双层磁电复合材料,并研究了Cr:BTO-TDF,Mn∶BTO-TDF,Co:BTO-TDF层状复合材料中的磁电效应.实验表明,在340×80 A·m^-1偏置磁场下, Cr:BTO-TDF的横向磁电电压系数达到最大值586 mV·cm^-1·(80 A·m^-1)^-1.在400×80 A·m^-1偏置磁场下,Mn∶BTO-TDF和Co:BTO-TDF的横向磁电电压系数的最大值分别为480 mV·cm^-1·(80 A·m^-1)^-1和445mV·cm^-1·(80 A·m^-1)^-1.研究表明掺杂BaTiO₃-TDF层状复合材料中具有较强的磁电耦合.作为无铅压电材料,掺杂BaTiO₃制备的磁电效应器件颇具应用前景. 关键词： 磁电效应 双层复合材料 3')" href="#">掺杂BaTiO₃ 1-xDy_xFe_2-y')" href="#">Tb_1-xDy_xFe_2-y     

Na4Ca3(AlO2)10∶Eu2+,Mn2+荧光粉的发光特性

采用高温固相法,制得一种新型荧光粉Na₄Ca₃(AlO₂)₁₀∶Eu²⁺,Mn²⁺。样品的结构和发光性质分别由X射线衍射谱和荧光光谱来表征。在Na₄Ca₃(AlO₂)₁₀∶Eu²⁺的激发光谱中出现了Eu²⁺的f-d跃迁吸收带;在发射光谱中,出现蓝光发射,峰值位于441 nm。当在Na₄Ca₃(AlO₂)₁₀∶Eu²⁺中掺杂Mn²⁺时,发生了Eu²⁺→Mn²⁺的能量传递,在542 nm处出现了Mn²⁺的发射峰。在Na₄Ca₃(AlO₂)₁₀∶Eu²⁺,Mn²⁺中,随着Mn²⁺浓度的增加,Eu²⁺粒子的发射强度减弱,而Mn²⁺粒子的发射强度增强,且Eu²⁺离子发射的衰减时间缩短,同时色度由蓝光移向白光。     

Filamentation-assisted fourth-order nonlinear process in KTP crystal

We present an experimental investigation of a filamentation-assisted fourth-order nonlinear optical process in KTP crystals pumped by intense 1.53~eV (807~nm) femtosecond laser pulses. Femtosecond light pulses at 2.58~eV (480~nm) are generated by the fourth-order nonlinear polarization (P⁴(ω ₂ ) = χ ⁴(ω ₂ ,ω ,ω ,ω ,- ω ₁ )E³(ω )E^* (ω ₁ ), where E(ω ) corresponds to the pump frequency and E(ω ₁ ) to the supercontinuum generated through filamentation). If the system is seeded by a laser beam at ω ₁ or ω ₂ and there are spatial and temporal overlaps with the pump beam, E(ω ₁ ) and E(ω ₂ ) are simultaneously amplified. When the intensity of the seed laser beam exceeds a certain intensity threshold, the contribution of P⁴(ω ) = χ ⁴(ω ,ω ₁ ,ω ₂ ,-ω, - ω )E(ω ₁ )E(ω ₂ )(E^* (ω))² becomes non-negligible, and the amplification weakens. The conversion efficiency from the pump to the signal at 2.58~eV (480~nm) attains to 0.1%.     

等离子体屏蔽效应对原子能级和振子强度的影响

利用Debye模型,研究了等离子体屏蔽效应对热等离子体中原子能级和振子强度的影响.通过在MCDF模型中引入等离子体屏蔽效应,计算了MnXXII-BrXXII等11个类Be离子在等离子体环境下2s²—［2s_1/2,2p_1/2］₁和2s²—［2s_1/2,2p_3/2］₁跃迁的能级和振子强度.计算结果表明,等离子体屏蔽效应使得类Be离子2s²—［2s_1/2,2p_1/2］₁跃迁的激发能量增大,从而导致谱线蓝移现象;并且随着屏蔽效应的不断增强,蓝移的程度会逐渐加大.屏蔽效应对于2s²—［2s_1/2,2p_3/2］₁跃迁的振子强度也有类似的影响. 关键词： Debye 等离子体屏蔽 跃迁能级 振子强度     

Ba3Tb(BO3)3 ∶Ce3+:一种白光LED用绿色荧光粉

采用高温固相法合成了Ba₃Tb(BO₃)₃和Ba₃Tb(BO₃)₃ ∶Ce³⁺两种绿色荧光粉,并研究了材料的发光性质.Ba₃Tb(BO₃)₃材料呈多峰发射,发射峰位于439,493,547,589和629 nm,分别对应Tb³⁺的⁵D关键词： 白光LED 3Tb(BO₃)₃')" href="#">Ba₃Tb(BO₃)₃ 3+')" href="#">Ce³⁺ 发光特性     

Spectroscopic parameters and molecular constants of HI(X~1Σ~+),DI(X~1Σ~+) and TI(X~1Σ~+) isotope molecules

The potential energy curve (PEC) of HI(X¹Σ⁺) molecule is studied using the complete active space self-consistent field method followed by the highly accurate valence internally contracted multireference configuration interaction approach at the correlation-consistent basis sets, aug-cc-pV6Z for H and aug-cc-pV5Z-pp for I atom. Using the PEC of HI(X¹Σ⁺), the spectroscopic parameters of three isotopes, HI(X¹Σ⁺), DI(X¹Σ⁺) and TI(X¹Σ⁺), are determined in the present work. For the HI(X¹Σ⁺), the values of D₀, D_e, R_e, ω_e, ω_eχ_e, α_e and B_e are 3.1551 eV, 3.2958 eV, 0.16183 nm, 2290.60 cm^-1, 40.0703 cm^-1, 0.1699 cm^-1 and 6.4373 cm^-1, respectively; for the DI (X¹Σ⁺), the values of D₀, D_e, R_e, ω_e, ω_eχ_e, α_e and B_e are 3.1965 eV, 3.2967 eV, 0.16183 nm, 1626.8 cm^-1, 20.8581 cm^-1, 0.0611 cm^-1 and 3.2468 cm^-1, respectively; for the TI (X¹Σ⁺), the values of D₀, D_e, R_e, ω_e, ω_eχ_e, α_e and B_e are of 3.2144 eV, 3.2967 eV, 0.16183 nm, 1334.43 cm^-1, 14.0765 cm^-1, 0.0338 cm^-1 and 2.1850 cm^-1, respectively. These results accord well with the available experimental results. With the PEC of HI(X¹Σ⁺) molecule obtained at present, a total of 19 vibrational states are predicted for the HI, 26 for the DI, and 32 for the TI, when the rotational quantum number J is equal to zero (J = 0). For each vibrational state, vibrational level G(?), inertial rotation constant B_? and centrifugal distortion constant D_? are determined when J = 0 for the first time, which are in excellent agreement with the experimental results.     

Sr3Gd0.5-xTb0.5(BO3)3∶xEu3+的发光性质及能量传递

采用高温固相法制备了Sr₃Gd_0.5-xTb_0.5(BO₃)₃∶xEu³⁺系列荧光粉,并研究了其发光性质与能量传递过程。Sr₃Gd_0.5-xTb_0.5(BO₃)₃∶xEu³⁺系列荧光粉在300~400 nm的近紫外光有效激发下产生489,544,594,614,624 nm的发射谱线,分别对应于Tb³⁺和Eu³⁺的特征跃迁。荧光寿命测试表明,随着Eu³⁺掺杂浓度的增大,Tb³⁺寿命逐渐缩短,证实该体系中存在Tb³⁺→Eu³⁺的能量传递过程,能量传递效率最大值为20.53%。在对Tb³⁺和Eu³⁺的能级结构进行分析的基础上,进一步探讨了Tb³⁺→Eu³⁺能量传递过程。Sr₃Gd_0.5-xTb_0.5-(BO₃)₃∶xEu³⁺系列荧光粉具有良好的红色发光性质,是潜在的可以应用于白光LED的光转换材料。     

Tc级数解的收敛性质

本文证明了,当|z_ph|c级数解的收敛圆是由奇点决定的,但是只要1/λ<[0.63+3μ⁺(1/Λ₁)] 1/(Λ₁),T_c级数解在收敛圆外仍然是个很好的渐近展开式,其中1/Λ₁=min(|z|,1);μ⁺(x)=(1-2μ^*x)μ^*。 关键词：