Electron Propagator Theory and Anion Electronic Structure

在这个由化学部理论和计算化学计划以及国际计划部美洲计划资助的项目中，Ortiz将使用新的量子力学方法解释几种不寻常阴离子的实验结果。 这项研究工作结合了新一代电子结构方法的发展，电子附着和分离过程的理论建模与计算，旨在测试这些方法和调查化学物质的实际利益。 开发的计算机代码将用于解决广泛的化学物种，包括“双里德伯”阴离子，两性离子，二价阴离子，聚阴离子和金属氧化物簇。 这些化学系统的研究需要实施和使用新的电子传播方法，可以处理电子相关的阴离子状态，以及伴随电子分离的大轨道弛豫效应。 准粒子自洽场方法扩展了现有的方法，满足了所研究系统的要求。 他们还提供了一个替代的电子结构的单电子图片，是由以前实现的理论所提供的补充。 该项目涉及与墨西哥城墨西哥国立自治大学的Ana Martinez及其同事的合作。拟议的研究涉及开发新的和改进的计算电离势和电子亲和势的算法。 对理论的挑战不是简单地再现一些测量的实验数据，而是开发一个理论模型，该模型与已知数据一致，并且能够预测随后测量的结果。 这里使用的传播子方法，特别是在定量独立粒子模型的新背景下，非常适合洞察力和理解力的发展。 由此产生的新的形式主义在这个项目中开发的承诺，提高精度，提高计算性能，更直接的解释计算数据。 这些方法将被应用到几个系统目前的实验兴趣，并将提供给公众一般使用。 将在墨西哥旅行并与外国合作者一起工作的学生将获得国际合作的经验，这将加强他们的科学和教育培训。

In this project funded by the Theoretical and Computational Chemistry Program of the Chemistry Division and the Americas Program in the Division of International Programs, Ortiz will interpret experimental results on several types of unusual anions using new quantum mechanical methodology. This research effort combines the development of a new generation of electronic structure methods for theoretical modeling of electron attachment and detachment processes with calculations that aim at testing these approaches and at investigating chemical species of practical interest. The computer codes developed will be used to address a wide range of chemical species, including "double Rydberg" anions, zwitterions, dianions, polyanions, and metal oxide clusters. Study of these chemical systems requires the implementation and use of new electron propagator methods that can treat electron correlation in anionic states as well as large orbital relaxation effects that accompany electron detachment. Quasiparticle self-consistent-field methods extend current techniques and satisfy the demands of the systems under study. They also offer an alternative one-electron picture of electronic structure that is complementary to that provided by previously implemented theories. This project involves a collaboration with Ana Martinez and her coworkers at UNAM in Mexico City.The proposed research involves the development of new and improved algorithms for calculating ionization potentials and electron affinities. The challenge to theory is not simply to reproduce a few measured experimental data, but rather to develop a theoretical model that is consistent with known data and capable of predicting consequences subject to subsequent measurement. The propagator method used here, especially in the novel context of a quantitative independent-particle model, is admirably suited to the development of insight and understanding. The resulting new formalisms developed in this project hold promise for enhanced accuracy, improved computational performance, and more straightforward interpretation of the computed data. These methods will be applied to several systems of current experimental interest and will be available to the public for general use. The students who will travel and work with the foreign collaborators in Mexico will gain experience with international collaboration that will enhance their scientific and educational training.