MCD spectra of biological molecules and functional molecules: theoretical study

(1)芳香族化合物的激发态对芳香族化合物的激发态、电离态和电子附着态进行了精确的理论光谱研究。SAC-CI方法重现了实验光谱的细节，并对噻吩类、吡啶类、对苯二酚类和苯胺类化合物提出了非常可靠和准确的指认。(2)基于有限微扰法的MCD理论在态总和方法的基础上对MCD谱进行了理论研究。在本研究中，MCD理论是用有限微扰方法建立的。用GUHF-SECI(广义无限制Hartree-Fock单激发组态相互作用)方法计算了相对论哈密顿量下的MCDA和B值.(3)MCD谱中的相对论效应GUHF-SECI方法应用于CH3X(X=F，Cl，Br，I)的MCD谱，并对相对论效应进行了评价.发现相对论效应是本质的，只有计入相对论效应才能再现这一趋势。(4)聚硅烷化合物具有S共轭的代表性激发光谱由于具有S共轭而表现出异常的光学性质。定量地再现了碳四硅烷的典型激发光谱。(5)激发态的分子结构和动力学研究发展了计算SAC-Cl分析能量梯度的稳定几何优化方法，并应用于一些有趣的体系。使用SAC-C1General-R方法开发了精确的理论光谱学。

(1) Excited states of aromatic compoundsAccurate theoretical spectroscopy has been performed for the excited, ionized, and electron-attached states of aromatic compounds. SAC-CI method reproduced the fine details of the experimental spectra and proposed very reliable and accurate assignments for the thiophene, pyridine, p-benzoquinone, and aniline etc.(2) MCD theory based on the finite perturbation methodMCD spectra have been theoretically studied on the basis of the sum-over-state method. In the present study, MCD theory has been formulated by the finite perturbation method. GUHF-SECI (generalized unrestricted Hartree-Fock-singly excited configuration interaction) method was adopted for calculating the MCD A and B values with the relativistic Hamiltonian.(3) Relativistic effect in the MCD spectraThe GUHF-SECI method has been applied to the MCD spectra of CH3X (X=F, Cl, Br, I) and the relativistic effect has been evaluated. The relativistic effect was found to be essential and the trend can be reproduced only by including the relativistic effect.(4) Representative excitation spectra originating s-conjugation of polysilane compoundsPolysilane compounds shows unusual optical properties since they have s-conjugation. Representative excitation spectra of carbotetrasilane originating the conformation of the Si-Si bond have been quantitatively reproduced.(5) Molecular structure and dynamics in the excited statesStable geometry optimization method calculating analytical energy gradients of SAC-Cl has been developed and applied to some interesting system. Accurate theoretical spectroscopy have been exploited using the SAC-C1 general-R method.