Ab Initio Electronic Structure Calculation of the Redox Potentials of Bacteriochlorophyll and Bacteriopheophytin in Solution
Ab Initio Electronic Structure Calculation of the Redox Potentials of Bacteriochlorophyll and Bacteriopheophytin in Solution
复制标题
溶液中细菌叶绿素和细菌脱镁叶绿素氧化还原电位的从头计算电子结构
DOI：
10.1021/j100044a042
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发表时间：
1995
期刊：
影响因子：
--
通讯作者：
R. Friesner
中科院分区：
文献类型：
--
作者：
L. Y. Zhang;R. Friesner
我们使用从头算电子结构代码PSGVB和精确的数值泊松-玻尔兹曼解算器对细菌叶绿素（BChl）和细菌叶绿素（BPh）分子在hartrei - fock水平上进行了自一致反应场（SCRF）计算。这是迄今为止进行的最大的从头算SCRF计算。我们计算了这些分子在DMF溶液中几种几何形状的氧化还原电位，并将结果与Fajer及其同事的实验结果进行了比较。由于忽略了电子相关性，绝对氧化还原能存在很大的误差，而相对氧化还原能与实验结果在质量上是一致的。溶剂化处理是预测BChl和BPh氧化还原能正确排序的关键。这些结果对计算光合反应中心的发色团的氧化还原能具有重要意义。参23。， 2个无花果。， 2个标签。
We have carried out self-consistent reaction field (SCRF) calculations on the bacteriochlorophyll (BChl) and bacteriopheophytin (BPh) molecules at the Hartree-Fock level using the ab initio electronic structure code PSGVB together with an accurate numerical Poisson-Boltzmann solver. These are by far the largest ab initio SCRF computations carried out to date. We calculate redox potentials of these molecules in DMF solution for several geometries and compare the results with experiments of Fajer and co-workers. While the absolute redox energies are substantially in error, due to neglect of electron correlation, the relative redox energies agree qualitatively with the experimental findings. Treatment of solvation is crucial in predicting the proper ordering of the BChl and BPh redox energies. These results have implications for calculation of redox energies of the chromophores in the photosynthetic reaction center. 23 refs., 2 figs., 2 tabs.