CAREER: Development and Application of First-Principles Dielectric Embedding Many-Body Perturbation Theory for Heterogeneous Interfaces

该职业奖支持计算和理论凝聚态物质和材料物理学的研究和教育。该项目的研究部分侧重于开发和应用新的计算工具来研究分子与固体基质之间形成的异质界面的电子性质。这种界面在能量转换材料中有广泛的应用，比如将太阳能转化为电流的光伏电池和光催化材料，这些材料可以收集太阳光来驱动化学反应。为了在基础水平上理解和控制这些复杂的过程，基于材料的量子力学模拟准确描述电子结构至关重要。考虑到系统的大尺寸和定量理解异质界面的能量转换机制所需的准确性，大多数传统的模拟方法要么效率低下，要么不准确。本项目研究部分的目标是开发一套新的计算方案，这些方案在异质分子-衬底界面的电子结构表征中既准确又有效。与目前的技术水平相比，这些方法将显著扩展可常规建模的材料和界面的范围。其基本思想是将接口划分为较小的组件或构建块，然后用高级理论处理每个组件，同时考虑将其嵌入到其他组件的环境中。使用这种嵌入方法，该团队将定量研究界面的每个组件的电子结构如何受到其他组件的影响，以及整个界面的电子结构与单个组件的电子结构有何不同。该团队将把新的计算方法应用于一些具有实验意义的新兴系统，特别是涉及多个光吸收器的界面，以及在不同方向测量时具有显着差异的电子和光学特性的界面。该研究将对能量转换机制和新能源材料的合理设计产生新的见解。研究活动与该项目的教育和推广部分紧密结合。PI将每年为密歇根东南部地区的当地高中生组织一次夏令营，以提高人们对计算重要性及其在科学研究中的作用的认识。夏令营还解决了底特律大都会地区在科学、技术、工程和数学方面的多样性挑战。此外，PI还将在其研究小组中为当地高中生和教师提供暑期实习职位，扩大PI在培养研究生以外培养下一代科学家方面的影响。此外，PI将继续在韦恩州立大学为本科生和研究生开设计算化学课程。PI将根据他在材料化学方面的研究专长不断增加课程内容，并根据入学学生的研究需求定制主题。此外，PI计划在韦恩州立大学化学系为本科生和研究生组织关于数学软件基本使用的小型讲习班，每年举办两次，以减轻学生在学习科学课程时普遍存在的数学焦虑。该职业奖支持计算和理论凝聚态物质和材料物理学的研究和教育。该项目的研究部分侧重于开发和应用新的计算方法来研究分子与固体衬底之间形成的非均相界面的准粒子电子结构和光学激发。这种界面在纳米级能量转换应用中无处不在，例如光伏和光催化。虽然多体微扰理论，如GW-BSE形式（G是格林函数，W是屏蔽的库仑相互作用，BSE代表贝特-萨尔皮特方程）提供了一个严格的理论框架，但大型分子-基质界面的第一性原理计算在计算上是昂贵的。缺乏有效而可靠的大型异质界面计算方案阻碍了对分子-基质相互作用和界面电荷动力学的基本理解。该项目的研究部分旨在开发一套新工具，称为“介电嵌入GW-BSE”，以便在不牺牲精度的情况下，对大型界面进行这种计算。其基本思想是将明确的GW-BSE计算限制在界面的每个组件内，同时将其他组件的影响视为介电环境。本项目将利用新开发的方法来研究一些具有实验意义的系统，包括：(1)单层过渡金属二硫族化合物（TMDs）和（金属）酞菁之间形成的界面，其中两组分的间隙和激子以及界面内TMD底物的谷假自旋将被研究；(2)涉及黑磷的界面，在这种界面上，介质屏蔽的各向异性将被仔细研究；(3)由界面调节的电荷转移系统，如吸附在金属或半导体衬底上的分子供体-受体对，以及吸附在具有层间电荷转移激子的双层tmd上的大型有机吸附剂。研究活动与该项目的教育和推广部分紧密结合。PI将每年为密歇根东南部地区的当地高中生组织一次夏令营，以提高人们对计算重要性及其在科学研究中的作用的认识。夏令营还解决了底特律大都会地区在科学、技术、工程和数学方面的多样性挑战。此外，PI还将在其研究小组中为当地高中生和教师提供暑期实习职位，扩大PI在培养研究生以外培养下一代科学家方面的影响。此外，PI将继续在韦恩州立大学为本科生和研究生开设计算化学课程。PI将根据他在材料化学方面的研究专长不断增加课程内容，并根据入学学生的研究需求定制主题。此外，PI计划在韦恩州立大学化学系为本科生和研究生组织关于Mathematica和WolframAlpha的小型讲习班，每年举办两次，以减轻学生在学习科学课程时常见的数学焦虑。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

NONTECHNICAL SUMMARYThis CAREER award supports research and education in computational and theoretical condensed matter and materials physics. The research part of this project focuses on the development and application of new computational tools to study the electronic properties of heterogeneous interfaces formed between molecules and solid substrates. Such interfaces find broad applications in energy conversion materials, such as photovoltaics that convert solar energy into electric current and photocatalytic materials that harvest solar light to drive chemical reactions. To understand and control these complex processes at a fundamental level, it is essential to accurately describe the electronic structure based on quantum mechanical simulations of the materials. Given the large system size and the accuracy needed to quantitatively understand the energy conversion mechanisms at heterogeneous interfaces, most conventional simulation methods are unfortunately either inefficient or inaccurate.The objective of the research part of this project is to develop a suite of new computational schemes that are both accurate and efficient in the characterization of the electronic structure at heterogeneous molecule-substrate interfaces. These methods will significantly expand the scope of materials and interfaces that can be routinely modeled as compared to the current state of the art. The basic idea is to divide the interface into its smaller constituents or building blocks and then treat each component with high-level theory while considering it embedded in the environment of the others. Using this embedding approach, the team will quantitatively investigate how the electronic structure of each component of the interface is affected by the others, and how the electronic structure of the entire interface is different from those of the individual constituents. The team will apply the new computational approach to a few emerging systems of experimental significance, especially interfaces involving multiple light absorbers and interfaces featuring electronic and optical properties which differ considerably when measured in different directions. The research will lead to new insights into energy conversion mechanisms and the rational design of new energy materials.The research activity is closely integrated with the education and outreach parts of this project. The PI will organize a summer camp annually for local high school students in the southeastern Michigan area, promoting the awareness of the importance of computation and its power in scientific research. The summer camp also addresses the diversity challenge in science, technology, engineering, and mathematics in the metropolitan Detroit area. Additionally, the PI will provide summer intern positions in his research group for local high school students and teachers, broadening the impact of the PI’s undertaking in educating the next generation of scientists beyond training graduate students. Furthermore, the PI will continue the development of a Computational Chemistry course at Wayne State University for both undergraduate and graduate students. The PI will continuously add course content based on his research expertise in materials chemistry and customize the topics to meet the research needs of the enrolled students. Moreover, the PI plans to organize mini-workshops on the basic use of mathematical software in the Chemistry Department at Wayne State University for both undergraduate and graduate students, offered twice a year, as an endeavor to mitigate the students’ common math anxiety in the learning of science courses.TECHNICAL SUMMARYThis CAREER award supports research and education in computational and theoretical condensed matter and materials physics. The research part of this project focuses on the development and application of new computational methods to study the quasiparticle electronic structure and optical excitations at heterogeneous interfaces formed between molecules and solid substrates. Such interfaces are ubiquitous in nanoscale energy conversion applications, such as photovoltaics and photocatalysis. Although many-body perturbation theory such as the GW-BSE formalism (G is the Green’s function, W is the screened Coulomb interaction, and BSE stands for Bethe-Salpeter equation) provides a rigorous theoretical framework, first-principles calculations of large molecule-substrate interfaces are computationally expensive. Lack of efficient yet reliable computational schemes for large heterogeneous interfaces hinders fundamental understanding of the molecule-substrate interactions and interfacial charge dynamics.The research part of this project aims to develop a suite of new tools, termed as “dielectric embedding GW-BSE”, to make such calculations practically affordable for large interfaces without sacrificing accuracy. The essential idea is to confine explicit GW-BSE calculations within each component of the interface while treating the effect of the others as a dielectric environment. This project will leverage the newly developed methods to study a few systems of experimental significance, including: (1) interfaces formed between monolayer transition-metal dichalcogenides (TMDs) and (metallo)phthalocyanines, where the gaps and excitons of both components as well as the valley pseudospin of the TMD substrates within the interface will be studied; (2) interfaces involving black phosphorus, where the anisotropy of the dielectric screening at such interfaces will be scrutinized; and (3) charge-transfer systems modulated by interfaces, such as molecular donor-acceptor pairs adsorbed on metal or semiconductor substrates and large organic adsorbates on bilayer TMDs featuring inter-layer charge-transfer excitons.The research activity is closely integrated with the education and outreach parts of this project. The PI will organize a summer camp annually for local high school students in the southeastern Michigan area, promoting the awareness of the importance of computation and its power in scientific research. The summer camp also addresses the diversity challenge in science, technology, engineering, and mathematics in the metropolitan Detroit area. Additionally, the PI will provide summer intern positions in his research group for local high school students and teachers, broadening the impact of the PI’s undertaking in educating the next generation of scientists beyond training graduate students. Furthermore, the PI will continue the development of a Computational Chemistry course at Wayne State University for both undergraduate and graduate students. The PI will continuously add course content based on his research expertise in materials chemistry and customize the topics to meet the research needs of the enrolled students. Moreover, the PI plans to organize mini-workshops on Mathematica and WolframAlpha in the Chemistry Department at Wayne State University for both undergraduate and graduate students, offered twice a year, as an endeavor to mitigate the students’ common math anxiety in the learning of science courses.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.