THEORETICAL STUDIES OF METALLOPROTEIN CHROMOPHORES

金属蛋白发色团的理论研究

• 批准号: 3298151
• 负责人: RICHARD A FRIESNER
• 金额: $ 9.75万
• 依托单位: COLUMBIA UNIV NEW YORK MORNINGSIDE
• 依托单位国家: 美国
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-07-01 至 1995-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3298151
• 关键词: Raman spectrometry; charge transfer complex; chlorophyll; chromophore; computer simulation; cytochrome P450; electric field; electronic spectra; heme; imidazole; ligands; mathematical model; metalloporphyrins; molecular dynamics; molecular energy level; mutant; oxidation reduction reaction; photosynthesis; physical model; porphyrin structure; site directed mutagenesis

This proposal describes theoretical studies of model porphyrin compounds and of the photosynthetic reaction center. The emphasis is on large scale ab initio electronic structure calculations for these systems using novel numerical techniques developed during the previous granting period which greatly reduce the computational effort needed to carry out high quality ab initio calculations for molecules containing 20-200 atoms. We will determine ground and excited state energies, redox potentials, equilibrium geometries, force fields, charge distributions, dispersion interactions, and-intermolecular electronic couplings for a wide variety of porphyrin moieties, including bacteriochlorophylls embedded in the reaction center protein environment. This information will then be used to calculate optical spectra and electron transfer dynamics in the photosynthetic reaction center, using theoretical methods for spectroscopic and quantum molecular dynamics simulations that we have developed over the past 10 years. We have proposed a simple physical model which explains the efficiency of charge separation in the reaction center and agrees qualitatively with the existing experimental data. The microscopic simulations described above will allow more quantitative models to be constructed, and will permit confirmation (or contradiction) of the basic picture that we have assembled on the basis of phenomenological modeling.

本方案描述了模型卟啉的理论研究。 化合物和光合作用反应中心。重点放在 这些体系的大尺度从头算电子结构计算 使用在前一次授予期间开发的新的数值技术 大大减少执行以下操作所需的计算工作量的时间段 含20-200个分子的高质量从头计算 原子。我们将确定基态和激发态的能量，氧化还原 势能，平衡几何，力场，电荷分布， 色散相互作用和分子间电子耦合 各种不同的卟啉部分，包括细菌叶绿素 嵌入在反应中心蛋白质环境中。 这些信息随后将被用于计算光谱和 光合作用反应中心的电子传递动力学，使用 光谱和量子分子动力学的理论方法 我们在过去10年里开发的模拟。我们有 提出了一个简单的物理模型来解释充电效率 在反应中心的分离，并在定性上符合 现有的实验数据。上述微观模拟 将允许构建更多的量化模型，并将允许 对我们已有的基本情况的确认(或矛盾) 在现象学模型的基础上组装而成。