Collaborative Research: Aggregation Mechanisms in Carbon Nanomaterials Based on Pi-conjugated Polycyclic Aromatic Hydrocarbons

合作研究：基于Pi共轭多环芳烃的碳纳米材料聚集机制

• 批准号: 2107820
• 负责人: Miklos Kertesz
• 金额: $ 28.39万
• 依托单位: Georgetown University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2107820&HistoricalAwards=false
• 关键词: Collaborative; Research; Aggregation; Mechanisms; Carbon

With support from the Macromolecular, Supramolecular, and Nanochemistry (MSN) Program of the Division of Chemistry, Professor Hans Lischka of Texas Tech University at Lubbock and Professor Miklos Kertesz of Georgetown University are studying the mechanisms of aggregation of individual polycyclic aromatic hydrocarbon molecules into assemblies. Polycyclic aromatic hydrocarbons are ubiquitous molecules that occur in practically all carbonaceous materials, including ones as familiar to the general public as soot. Facilitation as well as inhibition of aggregation requires understanding of the driving forces for this process at the molecular level. Such molecular level of understanding is central to the control of the formation of functional carbon nanomaterials and crucial for the rational development of organic semiconductors for application in electronic and optical technologies, such as organic solar cells, electronic sensors and quantum computing systems. During the course of conducting this collaborative project, graduate and undergraduate students from diverse backgrounds will be trained, and summer courses on the science of soft matter that are geared towards high school students will be conducted. The software protocols developed will be publicly shared with the scientific community and tutorials on quantum mechanical methods geared to the general public will be developed. The project addresses an urgently needed systematic study of the radical and biradical character of polycyclic aromatic hydrocarbon molecules and its role in their aggregation into nano-sized structures. Molecular level understanding of cluster formation is crucial for the rational development of organic nanocarbons for application in electronic and optical technologies. Computational modeling with highest-level quantum chemical methods (multireference theory) in combination with lower level, but computationally more efficient methods (ab initio single reference methods and density functional theory) will be employed. Descriptors will be used to construct and calculate promising dimer and trimer stacking combinations to evaluate the pancake interaction strength and compare them with experimental observations. These quantum chemical simulations will be extended by global modeling activities which will reflect in more detail the condensed phase structure based on the available interaction data of the quantum chemical calculations. This project includes collaboration with two experimental groups, providing structural and other characterization data. This project is expected to lead to a new and systematic approach to data collection based on computational work in the form of structural and energetic information with additional descriptors for biradical character. In the longer term, a better understanding of pancake bonding in the context of polycyclic aromatic hydrocarbons has the potential to provide important new insights into the mechanisms of radical and biradical aggregation.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.

在化学系高分子、超分子和纳米化学（MSN）项目的支持下，德克萨斯理工大学拉伯克分校的 Hans Lischka 教授和乔治城大学的 Miklos Kertesz 教授正在研究单个多环芳烃分子聚集成组装体的机制。 多环芳烃是普遍存在的分子，几乎存在于所有含碳材料中，包括像烟灰这样为公众所熟悉的材料。 聚集的促进和抑制需要在分子水平上了解该过程的驱动力。 这种分子水平的理解对于控制功能性碳纳米材料的形成至关重要，对于合理开发有机半导体在电子和光学技术（例如有机太阳能电池、电子传感器和量子计算系统）中的应用至关重要。 在开展这个合作项目的过程中，来自不同背景的研究生和本科生将接受培训，并将举办针对高中生的软物质科学暑期课程。 开发的软件协议将与科学界公开共享，并将开发面向公众的量子力学方法教程。 该项目致力于对多环芳烃分子的自由基和双自由基特征及其在聚集成纳米结构中的作用进行迫切需要的系统研究。 对簇形成的分子水平理解对于合理开发有机纳米碳在电子和光学技术中的应用至关重要。 将采用最高水平的量子化学方法（多参考理论）与较低水平但计算效率更高的方法（从头算单参考方法和密度泛函理论）相结合的计算建模。 描述符将用于构建和计算有希望的二聚体和三聚体堆叠组合，以评估煎饼相互作用强度并将其与实验观察结果进行比较。这些量子化学模拟将通过全局建模活动进行扩展，这些活动将根据量子化学计算的可用相互作用数据更详细地反映凝聚相结构。该项目包括与两个实验组的合作，提供结构和其他表征数据。该项目预计将带来一种新的、系统的数据收集方法，该方法基于结构和能量信息形式的计算工作，以及双自由基特征的附加描述符。从长远来看，更好地理解多环芳烃背景下的薄饼键合有可能为自由基和双自由基聚集机制提供重要的新见解。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Extremely Long C–C Bonds Predicted beyond 2.0 Å

超长 C–C 债券预计将超过 2.0 ×

• DOI: 10.1021/acs.jpca.3c01209
• 发表时间: 2023
• 期刊: The Journal of Physical Chemistry A
• 作者: Korpela, Eero J. J.;Carvalho, Jhonatas R.;Lischka, Hans;Kertesz, Miklos
• 通讯作者: Kertesz, Miklos

A Triply Negatively Charged Nanographene Bilayer with Spin Frustration

具有自旋受阻的三重负电荷纳米石墨烯双层

• DOI: 10.1002/anie.202217788
• 发表时间: 2022
• 期刊: Angewandte Chemie International Edition
• 作者: Wenqing Wang;Xiao-Hui Ma;Min Liu;Shuxuan Tang;Xuguang Ding;Yue Zhao;Yuan-Zhi Tan;Miklos Kertesz;Xinping Wang
• 通讯作者: Xinping Wang

Bonding and uneven charge distribution in infinite pyrene π-stacks

无限芘叠堆中的键合和不均匀电荷分布

• DOI: 10.1039/d2ce00933a
• 发表时间: 2022
• 期刊: CrystEngComm
• 影响因子: 3.1
• 作者: Flynn, Chase;Zhou, Zheng;McCormack, Megan E.;Wei, Zheng;Petrukhina, Marina A.;Kertesz, Miklos
• 通讯作者: Kertesz, Miklos