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MCD spectra of biological molecules and functional molecules: theoretical study

生物分子和功能分子的MCD谱：理论研究

基本信息

批准号：
13650883
负责人：
EHARA Masahiro
金额：
$ 2.3万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650883/
关键词：
Excited states MCD spectra SAC-Cl method Aromatic compounds Relativistic effect Ionized states Excited-state dynamics Finite perturbation method

项目摘要

(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.

(1)芳香族化合物的激发态芳香族化合物的激发态、电离态和电子附着态的精确理论光谱学已经完成。SAC-CI方法再现了实验光谱的细节，对噻吩、吡啶、对苯醌和苯胺等化合物的归属非常可靠和准确。(2)基于有限微扰法的MCD理论本文用状态求和法对MCD谱进行了理论研究。在本研究中，MCD理论已制定了有限摄动法。采用GUHF-SECI（广义非限制性Hartree-Fock-single excited configuration interaction）方法，由相对论哈密顿量计算了MCDA和B值。(3)用GUHF-SECI方法计算了CH_3X（X=F，Cl，Br，I）分子的MCD谱，并计算了相对论效应。相对论效应是必不可少的，只有考虑相对论效应才能再现这种趋势。(4)聚硅烷化合物的s-共轭激发光谱聚硅烷化合物具有s-共轭结构，因此显示出不寻常的光学性质。代表性的激发光谱的碳四硅烷起源的构象的硅-硅键已被定量再现。(5)本文发展了一种计算SAC-Cl分子解析能梯度的稳定几何优化方法，并将其应用于一些有趣的体系。使用SAC-C1通用R方法开发了准确的理论光谱学。