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.

在大分子，超分子和纳米化学（MSN）化学系的支持下，Lubbock的德克萨斯理工大学的Hans Lischka教授和乔治敦大学的Miklos Kertesz教授正在研究各个多环形芳族摩尔甲菌甲菌素的聚合机制。 多环芳烃是无处不在的分子，这些分子实际上是在所有碳质材料中发生的，包括公众熟悉的材料，如烟灰。 促进以及抑制聚集需要了解分子水平的该过程的驱动力。 这种分子的理解水平对于控制功能性碳纳米材料的形成至关重要，对于在电子和光学技术中应用有机半导体的合理发展至关重要，例如有机太阳能电池，电子传感器和量子计算系统。 在进行这个合作项目的过程中，将对来自不同背景的研究生和本科生进行培训，并将开展有关软件科学的夏季课程，这些课程将进行针对高中生的软件。 开发的软件协议将与科学界公开共享，并将开发有关向公众开发的量子机械方法的教程。 该项目涉及一项急需的系统研究，该项目对多环芳烃分子的自由基和异位特征及其在纳米大小结构中的聚集中的作用。 分子水平对簇形成的理解对于用于在电子和光学技术中应用有机纳米碳的合理发展至关重要。 将使用最高量子化学方法（多差距理论）结合较低级别的计算建模，但是将采用计算更有效的方法（从头开始单一参考方法和密度功能理论）。 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球建模活动扩展，该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结相结构。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。预计该项目将以结构性和能量信息的形式基于计算工作的新型和系统的数据收集方法，并具有其他关于Biradical特征的描述符。从长远来看，在多环芳族碳氢化合物的背景下，更好地理解煎饼粘结有可能提供对激进和Biradical聚合机制的重要新见解。该奖项反映了NSF的法定任务，并通过使用该基金会的知识绩效和广泛的影响来评估NSF的法定任务，并被认为是值得的。

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