Can (H2O) n (n = 1–2) as effective catalysts in the CH2OO + H2S reaction under tropospheric conditions?

The addition reaction of CH₂OO?+?H₂S → HSCH₂OOH without and with catalyst X (X?=?H₂O and (H₂O)₂) has been investigated by CCSD(T)-F12a/VTZ-F12//B3LYP/aug-cc-pVTZ method and canonical variational transition state theory with small curvature tunneling correction. When H₂O was introduced in the CH₂OO?+?H₂S reaction, it not only acts as a catalyst for producing HSCH₂OOH, but also plays as a reactant to forming HOCH₂OOH. The formation channel of HSCH₂OOH is more important than the formation channel of HOCH₂OOH with its calculated rate constant larger by 11.0–43.2 times within the temperature 280–320?K. Then, (H₂O)₂ catalysed CH₂OO?+?H₂S → HSCH₂OOH reaction has been taken into account with its rate lower 1.9–4.2 times than the reaction of CH₂OO?+?H₂S → HSCH₂OOH with water. Also, CH₂OO?+?H₂S with H₂O cannot compete with the CH₂OO?+?H₂S reaction without water. This is different from CH₂OO?+?(H₂O)₂ reaction, which is about 4 orders of magnitude larger than the rate constant for CH₂OO?+?H₂O reaction. Such discrepancy is possible because C(CH₂OO)···O(H₂O) interaction has been enhanced more obviously by H₂O as compared to that of C(CH₂OO)···O(H₂S) interaction.     

OCS经由F 31Π里德堡态生成CO(X1Σ+)+S(1D2)产物的波长相关性光解离

本文利用时间切片离子速度成像技术在134∽140 nm波段研究了OCS分子经由F 3¹Π里德堡态的真空紫外光解离动力学. 在选取的5个分别对应OCS(F 3¹Π, v₁=0∽4)的伸缩振动激发的光解波长,实验测得了来自CO(X¹Σ⁺)+S(¹D₂)产物通道的SS(¹D₂))实验影像,并获得了总平动能谱和CO(X¹Σ⁺, v)共生产物的振动布居及角分布. 结果分析表明OCS分子解离生成CO(X¹Σ⁺)+S(¹D₂)产物的过程经历了上态F 3¹Π 与C_?v和C_s构型的下电子态间非绝热耦合过程. 实验结果显示了很强的波长相关性：OCS (F 3¹Π, v₁)的较低转动激发态(v₁=0∽2)和较高转动激发态(v₁=3, 4)的CO(X¹Σ⁺)产物的振动布居和角分布具有显著差异,表明该解离过程中具有不同的解离机理. 本结果提供了振动耦合可能对真空紫外光解离动力学产生关键作用的相关证据.     

Network analysis of eigenvalue problem for multilayer dielectric waveguide consisting of arbitrary number of layers

In this paper, the eigenvalue problem of a multilayer dielectric waveguide consisting of arbitrary number of layers is solved by the microwave network method. A general program with the function of computer graphics has been developed for analyzing the dispersion characteristics and the electromagnetic field distributions of an N layer dielectric waveguide. As examples of practical applications of the program, first, the dispersions and field patterns for the planar waveguides with refractive index of parabolic and exponential profiles are analyzed. Secondly, the procedure of mode conversion and mode separation in dielectric branching waveguides is vividly demonstrated through analyzing the field distributions of asymmetric multilayer dielectric structures and the general rules of mode conversion are discussed. The examples show that the present method possesses the advantages of versatility, rapidity, simplicity and accuracy.     

硼玻璃中Sm3+离子的衰减及交叉弛豫

本文从Sm3+的衰减特性及能级跃迁性质两个方面研究Sm3+离子间的相互作用.一方面研究不同浓度Sm3+的衰减性质,利用Hirayama的理论确立相互作用的性质,另一方面研究相关能级的跃迁性质,从而证实由衰减所得结论的合理性.     

硼玻璃中Dy3+及Sm3+的辐射跃迁几率和无辐射跃迁几率

硼玻璃中掺杂Nd3+,Er3+,Tm3+等小能隙的稀土离子,由于硼玻璃声子能量大,多声子无辐射几率大,影响其发光效率。但由于硼玻璃熔点低,加工容易,对于民用上常用的Sm3+,Dy3+,Eu3+,Tb3+等大能隙物质,多声子无辐射跃迁不是主要因素的情况下,发光效率将如何是本文要研究的问题。另外,辐射跃迁性质的研究对于能量传递机理的研究也是很有意义的。     

Mn2+激活六角铝酸盐CeMgAl11O19-SrAl12O19固溶体的光谱学性质

本文研究(1-x)CeMgAl11O19-xSrAl12O19:Mn2+固溶体光谱学性质。Mn3+在固溶体中的荧光光潜由516nm绿色发射带和630-685nm红色发射带组成。前者归于占据4f格位的四面体Mn2+(g)离子,后者归于位于20格位的八面体Mn2+(r)中心。Mn2+(r)红色发射带随SrAl12O19含量增加而短移,x=0时,为685nm,x=0.8时,短移为630nm。固溶体中Ce3+-Mn2+(g和r)和Mn2+(g)-Mn2+(r)存在能量传递。荧光衰减分析表明,Mn2+(g)-Mn2+(r)能量传递是一种电偶极-电偶极相互作用的直接能量传递。随着固溶体中SrAl12O19含量的增加,Mn2+(g)-Mn2+(r)能量传递几率降低,临界距离R0减小。当x=0.8时,Mn2+(g)-Mn2+(r)传递消失。与之相反,Ce3+-Mn2+(g)能量传递则随SrAl12O19量的增高而加大。当x=0.8时,固溶体0.2CeMgAl11O19-0.8SrAl12O19:Mn2+中Ce2+-Mn2+(g)传递几率仅略低于商用荧光粉CeMgAl11O19中Ce3+-Tb3+传递几率。这类固溶体是有效的绿色发射荧光体。Mn2+格位(4f和2a)的晶场强度10Dq和Racah参数比C/B随SrAl12O19增加而呈减小趋势。本文表明,固溶体结构的镜面层对晶体光谱性质有大的影响。     

ZnS:Tm薄膜电致发光的激发过程

利用电子束蒸发方法制得ITO-Y2O3-ZnS:Tm3+-Y2O3-Al结构的薄膜可以得到蓝色电致发光.本文首次报导了ZnS:Tm3+薄膜与ZnS:Er3+、ZnS:Tb3+薄膜电致发光的激发过程有所不同.Tm3+离子的激发可以通过某些杂质中心到Tm3+离子的能量传递来实现.