A_a_1,A_a_2-B_b_1B_b_2缩聚反应的固化理论

本文讨论了A_(a_1),A_(a_2)-B_(b_1)B_(b_2)型缩聚反应的固化理论。给出了溶胶-凝胶分配公式、凝胶化条件、分布函数及适合固化全过程的高分子矩的循环公式和k次矩的解析表示式。     

关于反应途径Hamilton的性质

本文讨论了由Miller,Handy和Adams提出的反应途径Hamilton的向量丛结构。对N个原子构成的动力学体系,得到了向量丛有实正交群O(3N—7)对称性的结论。在(3N—7)的作用下,反应途径Hamilton的动能部分保持不变。本文还进一步讨论了Hamilton向量场的不变性。     

含有金属-金属键的双核原子簇离子体系[Mo~2Sn]^2-(n=6~9)的电子结构与电子光谱

使用SCF-CI方法研究了含有Mo-Mo单键的原子簇离子体系[Mo~2Sn](n=6~9)的电子结构及电子光谱。讨论了随n增加, 配体S, S~2, S~4对Mo-Mo键序、原子电荷的影响及其变化规律。分析了原子簇离子中的d-d相互作用能级次序及Mo-Mo, Mo-S'~t等键的性质, CI计算得到的谱带波数及强度次序与实验符合。指认分析表明, 谱带的跃迁性质是有趣的, 如第一吸收带为成键轨道之间的跃迁σ~x^2-y^2→σ~x~2(n=6~8), 同时, 对电子跃迁的性质进行了分类, 对谱带的电荷转移性质也进行了讨论。     

Cr3+离子配合物电子结构和d-d 跃迁谱的研究

建议了一种采用考虑重叠修正项的多重散射Ｘα自治场方法，结合不可约张量方法求解过渡金属配合物价电子体系多电子Ｓｃｈｒｏｄｉｎｇｅｒ方程的方法，并将其应用到Ｃｒ＾３＋配合物光谱的计算，其计算结果与实验结果的方均根偏差仅１．５ｋｃｍ＾－１，同时分析了Ｘα方法中重叠修正项对配合物电子结构以及光谱计算结果的影响，以及选用的组态对计算结果的影响。     

Structures and stabilities of HPS_2 isomers

The potential energy surface of HPS2 system containing nine isomers and fifteen transition states is obtained at MP2/6-311++G(d, p) and QCISD(t)/6-311++G(3df, 2p)(single-point) levels. On the potential energy surface, the lowest-lying frans-HSPS(EI) is found to be thermodynami-cally the most stable isomer followed by cis-HSPS(E2) and HP(S)S(C2v, E3) at 3.43 and 14.17 kJ/mol higher, respectively. The computed results show that species E1, E2, E3, stereo HP(S)S(Cs, E4) with PSS three-membered ring, isomers trans-HPSS(E5) and cis-HPSS(E6) which coexist with E4 are kinetically stable isomers. The products E6 and E5 in the reaction of HP with S2 can be isomerized into higher kinetic stable isomer E4 with 65.75 and 71.73 kJ/mol reaction barrier height, respectively. The predicated results may correct the possible inaccurate conclusion in that the product was experimentally assigned as isomer cis-HPSS(E6).     

掺Sn的纳米TiO2表面光致电荷分离及光催化活性

采用溶胶-凝胶法制备了不同掺Sn量的TiO₂纳米粒子, 主要利用表面光电压谱(SPS)和光致发光光谱(PL)对样品进行了表征, 并通过光催化降解苯酚实验来评估样品活性. 重点考察了热处理温度和掺Sn量对样品表面光生载流子的分离及光催化活性的影响, 并探讨了Sn使TiO₂纳米粒子改性的机制. 结果表明, 在适当温度处理下, 适量Sn的掺入能够有效促进TiO₂纳米粒子表面光生载流子的分离, 以至于使其光催化活性得到显著提高.     

正八面体过渡金属化合物能谱的理论计算Ⅱ.

本文提出了在非限制Hartree-Fock方法计算的分子轨道基础上,计算分子价电子体系能谱和多电子状态的不可约张量方法。使用这种方法,计算了具有近似正八面体对称性的过渡金属化合物MnBr_6~(4-)、MnCl_6~(4-)、FeCl_6~(3-)、MnF_6~(4-)、Mn(H_2O)_6~(2+)、Co(NH_3)_6~(3+)、NiF_6~(4-)、Ni(H_2O)_6~(2+)、Ni(NH_3)_6~(2+)的d-d跃迁能谱。理论计算结果与实验符合较好,误差为若干k cm~(-1)     

Ultrahigh Harmonic Generation from an Atom with Superposition of Ground State and Highly Excited States

We investigate the high-order harmonic generation from an atom prepared in a superposition of ground state and highly excited state. When the atom is irradiated by an ultrashort pulse, the cutoff position of the plateau in the harmonic spectrum is largely extended compared with the case that the atom is initially in the ground state. The physics of the extension of the high-order harmonic plateau can be interpreted by the spatial structure of the atomic initial wave packet. We can optimize the generation of high-order harmonics by substituting the excited state for a particular coherent superposition of some highly excited states to form a spatially localized excited wave packet.     

Theoretical study on second-order nonlinear optical properties of unsymmetric bis (phenylethynyl) benzene series derivatives

On the basis of ZINDO methods, according to the sum-overstates (SOS) expression, the program for the calculation of the second-order nonlinear optical susceptibilities βijk and βμ of molecules was devised, and the structures and nonlinear optical properties of unsymmetric bis (phenylethynyl) benzene series derivatives were studied. The influence of the molecular conjugated chain lengths, the donor and the acceptor on βμ was examined.     

碱金属化物M+aza222M′- (M,M′=Li,Na, K)的结构及非线性光学性质

采用密度泛函理论(DFT)B3LYP方法得到具有有机穴状配体的碱金属化物M+aza222M′-(M,M′=Li,Na,K)的几何结构.并使用了BHandHLYP方法计算了此体系的非线性光学(NLO)性质.结果表明:该体系具有很大的一阶超极化率(β0),对于Li+aza222K-体系,β0值达到1.0×106a.u.;体系的β0值及配体aza222内外的碱金属之间距离与碱金属的原子序数均存在着依赖关系.通过与其它碱金属化物的β0值对比发现,aza222配体能够显著增大碱金属化物的一阶超极化率.