B32及其包心化合物的电子结构与电子光谱的理论预测

在ＩＮＤＯ／ＣＩ方法的基础上，预测Ｂ３２及其包心化合物的电子结构与光谱，并与其共轭多面体Ｃ４０及其包心化合物进行对比。     

CNDO/2 and INDO all-valence-electron calculations on the dipole moment of iodine compounds

An application of the semi-empirical CNDO/2 and INDO methods to calculate the molecular dipole moment of iodine compounds has been made with all-valence electron scheme. Equilibrium geometries are obtained using experimental bond lengths and the various semi-empirical parameters required inscf-mo scheme are obtained from atomic Hartree-Fock calculations and by comparison withab initio calculations. Bothsp andspd valence basis sets are used.     

Effect of Substituting Group on the Calculated Nonlinear Second－Order Optical Susceptibilities of Substituted Thiophene Derivatives with Quinoidlike Conformation

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The spectroscopy, dynamics, and electronic structure of pyrenyl-dU nucleosides: P/dU charge transfer state photophysics

Various spectroscopies including UV-vis absorbance, emission, and emission quantum yield are combined with a variety of kinetics measurements including time resolved emission and nanosecond, picosecond, and femtosecond transient absorbance (TA) to systematize the P⁺/dU⁻ charge transfer (CT) state dynamics of a variety of pyrenyl-dU nucleoside conjugates in several solvents of varying polarity. These results are then analyzed further by means of electronic structure computations in vacuum and using two different solvent models. Finally, the excess electron dynamics of a number of DNA duplex structures substituted with two different pyrenyl-dU nucleosides and 5-XdU, where X=Br or F, electron traps are discussed in terms of achieving high yields of long-lived photoinduced CT products in DNA.     

双核金属酞菁类化合物催化脱硫机理研究Ⅲ──M（Ⅱ）Pc－PcM（Ⅱ）的电子结构及M（Ⅱ）与Pc间的键合方式

采用ＩＮＤＯ／Ｓ方法研究了双核金属酞菁类化合物Ｍ（Ⅱ）Ｐｃ－ＰｃＭ（Ⅱ）（Ｍ＝Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ）的电子结构．结果表明当金属离子Ｍ（Ⅱ）与酞菁环键合后，其价电子重新布居，从而导致在Ｍ＝Ｃｒ、Ｍｎ、Ｆｅ、Ｚｎ时中心金属离子从酞菁环得到电子；而当Ｍ＝Ｃｏ、Ｎｉ、Ｃｕ时却是中心金属离子向酞菁环转移电子．键合方式的研究结果表明在Ｍ（Ⅱ）Ｐｃ－ＰｃＭ（Ⅱ）分子中，中心金属离子与酞菁环间存在着σ配键、反馈π键和离域π键三种化学键形成，从而在中心金属离子与酞菁环间产生灵活的“电荷呼吸”作用，构成了双核金属酞菁类化合物氧化还原作用的基础．     

几种C_(60)环加成物的结构及光谱的理论研究

用INDO系列方法研究了C60的几种环加成衍生物C68H8、C68H6O、C68H4O2的结构和UV谱．结果表明，C68H8的［6，6］异构体的船式构象比平面构象稍稳定，两者能量差为9．6kJ／mol；而随着衍生物中羰基的增加，C60母体也由电子受体变为电子给体．以优化构型为基础，计算产物的UV谱，对电子跃迁进行理论指认，并分析了光谱红移的原因．     

Application of molecular models to electronic structure calculations of defects in oxide crystals. I. Parametrization of the modified INDO method

A modified calculation scheme of the INDO method is applied for calculating the electronic structure of perfect and imperfect oxide crystals. In order to obtain a flexible scheme permitting reliable calculation of both the electronic structure and the defect conformations, the INDO parameters for H, Li, Mg, Si, O are fitted directly to reproduce one-electron energies as well as the vicinity of the potential energy curve minima for a series of diatomic molecules and the electronic structure of MgO and -crystoballite form of SiO₂. The method is tested on the Li₂SiO₃ crystal calculated within the framework of the large unit cell model.     

C77Si电子结构和光谱的量子化学研究

用INDO系列方法对C77Si的21种可能异构体进行了理论研究,表明最稳定异构体是由C78(C2v)椭球长轴所穿过的六元环上原子C35被Si取代所形成的,椭球短轴附近的原子不宜被取代;C77Si光谱吸收峰与C78相比发生红移,讨论了吸收峰红移的原因.     

Porphyrins 42. Ground and excited state calculations on the isomers of free base porphine and sirohydrochlorin

Symmetry instabilities were encountered during MINDO/3 geometry optimizations of the sirohydrochlorin and porphine isomers leading to bond alternating optimal structures. Transition energies and oscillator strengths were calculated with INDO/S/CI. Our calculations predict the ground state cis and trans isomers of sirohydrochlorin to be close in energy and confirm the experimental assignment of the absorptions bands, with the cis tautomer having a red shifted spectrum.Part 41. Gouterman, M., Sayer, P., Shankland, E., Smith, J. P.: Inorg. Chem. 20, 87 (1981)     

2,5-取代基-3,4-C60吡咯衍生物的电子光谱和非线性光学性质规律的理论研究

利用量子化学半经验AM1及ZINDO方法研究了2,5-取代基-3,4-C60吡咯衍生物的结构规律和光谱性质.以全自由度优化几何构型为基础,计算了化合物的电子光谱.几种化合物在400 nm以上均产生非C60特征吸收,结果与实验值一致,并对电子跃迁进行了指认,分析了光谱红移的原因.同时用INDO/CI-SOS方法计算了它们的二阶非线性光学系数,其βμ值在-30.14×10-30～-65.49×10-30 esu之间.