Ab Initio Electron Propagator Calculations on Molecular Anions

J. Vincent Ortiz由理论与计算化学项目资助，对分子阴离子进行从头算电子传播体计算。Ortiz将对P3自能近似进行一些方法和算法上的改进，包括开发该算法的并行版本。将电子传播子理论扩展到处理电子亲和、光电子能谱震荡、核心电离能和俄歇能谱。为了提供与电子结构理论的其他量子力学方法的联系，Ortiz还将开发解释工具，如有效哈密顿量的提取，以及基于电子密度和局部相关势的基态相关能的解释。应用包括：1)水-尿嘧啶阴离子配合物可能的偶极结合态和价结合态的检验，以解释与里德伯态高激发原子的光电子能谱和电荷交换碰撞；2)金属碳化物阴离子的离子丰度行为及热化学研究；3)双Rydberg阴离子的光电子能谱、结构和能量性质的预测。Ortiz提出的理论方法的发展将有助于所有领域的研究人员对技术上重要的分子物种的分子和离子性质进行准确的计算。

J. Vincent Ortiz is funded by a grant from the Theoretical and Computational Chemistry program to perform ab initio electron propagator calculations on molecular anions. Ortiz will make a number of methodological and algorithmic improvements in the P3 self-energy approximation including the development of a paralellized version of the algorithm. Extensions of the electron propagator theory to the treatment electron affinities, shake-ups in photoelectron spectra, core ionization energies, and Auger spectra will also be pursued. In an effort to provide links to other quantum mechanical approaches to electronic structure theory, Ortiz will also develop interpretive tools such as the extraction of effective Hamiltonians, and an interpretation of ground state correlation energies based on electron density and local correlation potential. Applications include: 1) an examination of possible dipole-bound and valence-bound states of water-uracil anionic complex to explain photoelectron spectra and charge exchange collisions with highly excited atoms in Rydberg states; 2) a study of the ionic abundance behavior and thermochemistry of metal carbide anions; and 3) a prediction of the photoelectron spectra, structures and energetic properties of double Rydberg anions.Development of theoretical methods such as those proposed by Ortiz will help researchers in all fields to perform accurate calculations of the molecular and ionic properties of technologically important molecular species.