甲的内部球电子转移重组能量是甲的能量
Xenia Amashukeli1, Nadine E Gruhn, Dennis L Lichtenberger
1Division of Chemistry and Chemical Engineering and the Beckman Institute, California Institute of Technology, Pasadena, CA 91125, USA.
Journal of the American Chemical Society
|November 26, 2004
概括
用光电子光谱测量了色素中的电子转移重组能量. 氧化后的结构变化主要发生在氨酸环内,不受替代剂或环境的显著影响.
科学领域:
- 无机化学 无机化学
- 物理化学 物理化学
- 频谱学是一种光谱学.
背景情况:
- 电子转移过程在化学和生物学中是基本的.
- 了解重组能量对于预测电子转移速率至关重要.
- 色氨酸在生物系统和催化过程中很重要.
研究的目的:
- 实验性地确定Zn ((protoporphyrin IX) 和Zn ((octaethylporphyrin)) 的内部球体重组能量.
- 研究氨酸环内的结构变化与外部因素对重组能量的贡献.
- 评估用于预测这些能量的计算模型的适用性.
主要方法:
- 采用了气相价值光电子光谱学.
- 第一次电离的带形分析被用来确定重组能量.
- 与各种计算模型进行了比较.
主要成果:
- 通过实验确定了自我交换的内部球的总重组能量为120-140 meV.
- 氧化后的结构变化主要局限于氨酸环.
- 替代品和环境因素对重组能源的贡献最小.
结论:
- 氨酸环结构决定了对电子转移重组能量的主要贡献.
- 准确的低重组能量的计算预测需要仔细的模型选择.
- 混合的Hartree-Fock/DFT函数对这些系统的建模非常有前途.
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