Renormalized Electron Propagator Theory: Development, Application and Interpretation

在化学系的理论和计算化学项目中，Ortiz教授将把电子传播子理论应用于小分子电子结构的计算。这些计算将有助于解释许多有趣的原子和分子系统的电子结构和成键。电子传播子理论通过精确计算电子结合能和费曼-戴森振幅，提供了一个相互关联的单电子成键图像。对现有代码的改进将集中在传播子重新正规化上。参考态平均值将通过使用来自耦合团簇单态和双态计算的振幅来改进，并进行一定的无穷级修正。用基于逆迭代法的算法对超算符哈密顿矩阵进行对角化将导致算子流形的重整化。完全的双电子转换将促进对大分子的计算，并与其他程序接口。对于聚硅烷齐聚物，单电子态和能量与链长和局部构象的依赖关系将被探索。研究了半金属有机化合物的键能和电离能之间的关系。三原子自由基中的非共振发射将通过计算基态和激发态势能面来考虑。各种双里德堡阴离子的稳定性的解释将通过单电子图片来寻找。

With this grant in the Theoretical and Computational Chemistry Program of the Chemistry Division Professor Ortiz will apply electron propagator theory to the computation of the electronic structure of small molecules. The computations will aid in the interpretation of the electronic structure and bonding of many interesting atomic and molecular systems. Electron propagator theory provides a correlated one-electron picture of bonding through accurate calculations of electron binding energies and Feynman-Dyson amplitudes. Improvements to existing codes will concentrate on propagator renormalizations. Reference state averages will be improved with certain infinite order corrections by employing amplitudes from coupled cluster singles and doubles calculations. Diagonalization of the superoperator Hamiltonian matrix with an algorithm based on inverse iterations will result in operator manifold renormalizations. Full two-electron transformations will facilitate calculations on large molecules and interface with other codes. The dependence of one-electron states and energies on chain length and on local conformations will be explored for polysilane oligomers. Relationships between bond energies and ionization energies will be studied for half-sandwhich organometallics. Nonresonant emissions in triatomic radicals will be considered through calculations of ground and excited state potential energy surfaces. Explanations for the stabilities of various double Rydberg anions will be sought through one electron pictures.