Renormalized Electron Propagator Theory: Development, Application and Interpretation

在化学系理论与计算化学项目的资助下，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。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关的单电子成键图。对现有代码的改进将集中在传播器重整化上。参考状态平均值将通过使用来自耦合簇单次和双次计算的振幅进行一定的无限阶修正来改进。用基于逆迭代的算法对角化超算子哈密顿矩阵将导致算子流形的重整化。完整的双电子转换将有助于大分子的计算和与其他代码的接口。将探讨聚硅烷低聚物的单电子态和能量对链长和局部构象的依赖性。本文将研究半砂有机金属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。对各种双里德堡阴离子稳定性的解释将通过一个电子图来寻求。

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.