Non-Hermitian Quantum Mechanics in Electronic-Structure Theory

电子结构理论中的非厄米量子力学

• 批准号: 387825248
• 负责人: Professor Dr. Thomas-Christian Jagau
• 金额: --
• 依托单位: Department of Chemistry
• 依托单位国家: 德国
• 项目类别: Independent Junior Research Groups
• 财政年份: 2017
• 资助国家: 德国
• 起止时间: 2016-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/387825248?language=en
• 关键词: Non; Hermitian; Quantum; Mechanics; Electronic

The goal of the research is to establish non-Hermitian quantum mechanics as a powerful and versatile tool in quantum chemistry. Novel wave-function based electronic-structure methods shall be developed that will enable the treatment of electronic resonances, that is, solutions of the time-independent Schrödinger equation with complex energy, in close analogy to bound states. These theoretical developments shall be combined with efficient computer code implementations and computational studies. Four main research directions are proposed: 1) characterization of the complex-valued potential energy surfaces (CPES) of polyatomic temporary radical anions, both on the basis of the Franck-Condon principle and beyond the Franck-Condon region by studying nuclear dynamics on CPES; 2) development and application of electronic-structure methods for autoionizing species with different electronic structure than radical anions, in particular Feshbach resonances and closed-shell dianions; 3) development and application of electronic-structure methods for molecular strong-field ionization and high-harmonic generation, in particular investigation of field-induced changes in molecular structure and properties; 4) modeling charge transport through molecular junctions within the quasistatic approximation by means of source-sink potentials. The research will exploit for the first time the remarkable isomorphism between these phenomena, i.e., that they are all governed by electronic resonances, and make them amenable to high-accuracy quantum-chemical calculations. In this way, a better understanding of a variety of questions that are not answered in a satisfactory way by currently available theoretical approaches will be gained. Respective areas of application are, for example, dissociative electron attachment, molecular high-harmonic generation, and the conductance of single molecules.

该研究的目标是将非厄米量子力学建立为量子化学中强大而通用的工具。应开发新的基于波函数的电子结构方法，使电子共振的处理成为可能，即具有复杂能量的时间无关Schrödinger方程的解，与束缚态非常相似。这些理论发展应与有效的计算机代码实现和计算研究相结合。提出了四个主要的研究方向：1)基于Franck-Condon原理和超越Franck-Condon区域研究多原子暂时自由基阴离子的复值势能面（CPES）；2)电子结构方法的发展与应用，研究了与自由基阴离子不同电子结构的自电离物质，特别是Feshbach共振和闭壳离子；3)分子强场电离和高谐波产生的电子结构方法的发展和应用，特别是对分子结构和性质的场致变化的研究；4)利用源-汇电位模拟准静态近似下分子结的电荷输运。这项研究将首次利用这些现象之间显著的同构性，即它们都由电子共振控制，并使它们适用于高精度的量子化学计算。通过这种方式，可以更好地理解目前可用的理论方法无法以令人满意的方式回答的各种问题。相应的应用领域是，例如，解离电子附着，分子高谐波的产生，和单分子的电导。

项目成果

Coupled-cluster treatment of molecular strong-field ionization.

分子强场电离的耦合簇处理

• DOI: 10.1063/1.5028179
• 发表时间: 2018
• 期刊: The Journal of chemical physics
• 作者: T.-C. Jagau

Characterization of the vibrational properties of copper difluoride anion and neutral ground states via direct and indirect photodetachment spectroscopy.

通过直接和间接光脱离光谱表征二氟化铜阴离子和中性基态的振动特性

• DOI: 10.1063/1.5040122
• 发表时间: 2018
• 期刊: The Journal of chemical physics
• 作者: J. Lyle;S. R. Chandramoulee;J. Hamilton;B. Traylor;T. Guasco;T.-C. Jagau;R. Mabbs
• 通讯作者: R. Mabbs

A Schwarz inequality for complex basis function methods in non-Hermitian quantum chemistry.

非厄米量子化学中复杂基函数方法的施瓦茨不等式

• DOI: 10.1063/1.5123541
• 发表时间: 2019
• 期刊: The Journal of chemical physics
• 作者: T. H. Thompson;C. Ochsenfeld;T.-C. Jagau
• 通讯作者: T.-C. Jagau

Resolution-of-the-identity approximation for complex-scaled basis functions.

复尺度基函数的恒等近似解析

• DOI: 10.1063/1.5119695
• 发表时间: 2019
• 期刊: The Journal of chemical physics
• 作者: M. Hernández Vera;T.-C. Jagau
• 通讯作者: T.-C. Jagau