Understanding Excimers in Molecular J- and H-aggregates: A Holstein-Peierls Approach
了解分子 J 和 H 聚集体中的准分子:荷斯坦-佩尔斯方法
基本信息
- 批准号:2221923
- 负责人:
- 金额:$ 38.1万
- 依托单位:
- 依托单位国家:美国
- 项目类别:Standard Grant
- 财政年份:2023
- 资助国家:美国
- 起止时间:2023-06-01 至 2026-05-31
- 项目状态:未结题
- 来源:
- 关键词:
项目摘要
NONTECHNICAL SUMMARY This award supports theoretical/computational research and education on how light interacts with semiconductor materials made of organic molecules. The more familiar semiconductors like silicon, which is widely used in microelectronics and computer chips, are inorganic. However, semiconductors based on organic molecules offer advantages such as less expensive materials processing and more favorable mechanical properties. Organic materials continue to make inroads into commercial devices, such as organic light-emitting diodes or OLEDs used in displays (the “OLED” TV), solar cells, which convert sunlight into electrical energy, and even “wearable” electronic devices and sensors. The PI and his research team will investigate fundamental processes such as light absorption and light emission in organic crystals and aggregates, as well as how the energy from light absorption is transported between molecules - similar to what occurs in plants during the process of photosynthesis. The research team will conduct a theoretical investigation by solving equations based on quantum mechanics which describe how organic molecules respond to light. The equations will be solved using sophisticated computer algorithms. Of particular interest are certain electronic excited states known as excimers, which emit light of longer wavelengths and convert electronic energy into light energy less efficiently. The PI and his team will study how such excimers form and ultimately how to design molecular aggregates which avoid excimer formation. The proposed activities will also enhance research infrastructure through collaborations with experimentalists such as Professor Libai Huang at Purdue University, who will employ state-or-the-art experimental techniques to probe energy transport in organic films. Overall, this research effort should contribute to a blueprint for the next generation of electronic devices based on organic materials.TECHNICAL SUMMARY This award supports theoretical and computational research and education on how light is absorbed or emitted from semiconductor materials made of organic molecules. Solid phases of pi-conjugated molecules and polymers continue to receive widespread attention as semiconducting materials in field effect transistors, light emitting diodes, and solar cells. However, despite the more than five decades of intensive experimental and theoretical research following Kasha's pioneering work on molecular H- and J-aggregates, important questions remain regarding the fate of photo-excitations and how their spectral signatures depend on crystal packing and morphology. The PI’s group has extended Kasha’s model, which is predicated entirely on long-range Coulombic coupling, to include short-range (super-exchange) coupling arising from intermolecular charge-transfer, as well as local coupling to the vinyl-stretching mode responsible for pronounced vibronic progressions in the UV-Vis spectra of a great many conjugated molecules. Although the model can predict with quantitative accuracy details of the absorption spectral line shape and correlate spectral features to the nature of the underlying excitons, it is limited in its ability to describe photoluminescence and energy transport, processes which often require the inclusion of excimers. Excimers, common in pi-conjugated molecules, arise when an electronic excited state relaxes along a “slow” intermolecular (phonon) coordinate resulting in featureless, red-shifted emission. In this project, the next generation of molecular H- and J-aggregate models will be developed which account for excimer formation and emission. The approach is based on a Holstein-Peierls Hamiltonian which includes electronic coupling along the slow-coordinate, is particularly strong in closely packed systems like π-stacks, where the intermolecular electron and hole transfer integrals are hypersensitive to small, sub-Angstrom, changes in the relative orientation of neighboring chromophores. The Holstein-Peierls approach enables all of the important physical processes to be treated on equal footing and fully quantum-mechanically. The model will be employed to account for the absorption and photoluminescence spectral line shapes in excimer-forming perylene diimide dimer complexes and larger π-stacks. The ability of excimers to function as energy traps will be investigated through analysis of the density matrix equations of motion. Libai Huang at Purdue University will collaborate and provide experimental validation by conducting spectroscopic measurements and femtosecond-resolved transport measurements of several perylene diimide derivatives which display varying degrees of excimer emission. The PI’s approach may enhance the likelihood for discovering new and potentially useful physical phenomena, as well as design strategies for controlling excimer formation for device applications.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.
该奖项支持关于光如何与有机分子制成的半导体材料相互作用的理论/计算研究和教育。更熟悉的半导体,如硅,广泛用于微电子和计算机芯片,是无机的。然而,基于有机分子的半导体提供了诸如更便宜的材料加工和更有利的机械性能等优点。有机材料继续进入商业设备,如显示器中使用的有机发光二极管或OLED(“OLED”电视),将阳光转化为电能的太阳能电池,甚至“可穿戴”电子设备和传感器。PI和他的研究团队将研究有机晶体和聚集体中的光吸收和光发射等基本过程,以及光吸收的能量如何在分子之间传输-类似于植物在光合作用过程中发生的情况。研究小组将通过求解基于量子力学的方程进行理论研究,这些方程描述了有机分子如何对光做出反应。这些方程将用复杂的计算机算法来求解。特别感兴趣的是被称为准分子的某些电子激发态,其发射较长波长的光并且较低效率地将电子能量转换成光能。PI和他的团队将研究这些准分子是如何形成的,并最终研究如何设计避免准分子形成的分子聚集体。拟议的活动还将通过与普渡大学黄立白教授等实验学家的合作来加强研究基础设施,他将采用最先进的实验技术来探测有机薄膜中的能量传输。总的来说,该研究成果将为基于有机材料的下一代电子设备的蓝图做出贡献。技术概要该奖项支持关于有机分子构成的半导体材料如何吸收或发射光的理论和计算研究以及教育。π共轭分子和聚合物的固相作为场效应晶体管、发光二极管和太阳能电池中的半导体材料继续受到广泛关注。然而,尽管在Kasha对分子H-和J-聚集体的开创性工作之后进行了五十多年的深入实验和理论研究,但关于光激发的命运以及它们的光谱特征如何取决于晶体堆积和形态的重要问题仍然存在。PI的小组已经扩展了Kasha的模型,该模型完全基于长程库仑耦合,以包括由分子间电荷转移产生的短程(超交换)耦合,以及与乙烯基拉伸模式的局部耦合,该模式负责许多共轭分子的UV-Vis光谱中的显著振动进展。虽然该模型可以定量准确地预测吸收光谱线形状的细节,并将光谱特征与底层激子的性质相关联,但它在描述光致发光和能量传输过程中的能力有限,这些过程通常需要包含准分子。在π共轭分子中常见的准分子,当电子激发态沿着“慢”分子间(声子)坐标沿着弛豫时产生,导致无特征的红移发射。在这个项目中,下一代的分子H-和J-聚集体模型将开发占激基缔合物的形成和排放。该方法基于Holstein-Peierls哈密顿量,其包括沿着慢坐标的电子耦合沿着,在紧密堆积的系统如π堆叠中特别强,其中分子间电子和空穴转移积分对相邻发色团的相对取向的小的亚埃变化非常敏感。Holstein-Peierls方法使所有重要的物理过程都能在平等的基础上被完全量子力学地对待。该模型将被用来解释吸收和光致发光光谱线形状的准分子形成的二聚体配合物和较大的π堆叠。准分子作为能量陷阱的能力将通过分析密度矩阵运动方程来研究。普渡大学的Libai Huang将通过对几种显示不同程度准分子发射的二萘嵌苯二酰亚胺衍生物进行光谱测量和飞秒分辨传输测量进行合作并提供实验验证。PI的方法可能会提高发现新的和潜在有用的物理现象的可能性,以及为设备应用控制准分子形成的设计策略。该奖项反映了NSF的法定使命,并已被认为是值得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的支持。
项目成果
期刊论文数量(1)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
A Holstein-Peierls Approach to Excimer Spectra: The Evolution from Vibronically Structured to Unstructured Emission
- DOI:10.1021/acs.jpcc.1c10255
- 发表时间:2022-03-03
- 期刊:
- 影响因子:3.7
- 作者:Bialas, April L.;Spano, Frank C.
- 通讯作者:Spano, Frank C.
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{{ truncateString('Francis Spano', 18)}}的其他基金
Modeling Molecular Aggregate Photophysics in Free Space and in Optical Microcavities
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$ 38.1万 - 项目类别:
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1603461 - 财政年份:2016
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Excitonic Coupling in Molecular and Polymeric Aggregates: Beyond Conventional J- and H-aggregation
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1505437 - 财政年份:2015
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$ 38.1万 - 项目类别:
Continuing Grant
DMREF - Collaborative Research: Developing design rules for enhancing mobility in conjugated polymers
DMREF - 协作研究:开发增强共轭聚合物迁移率的设计规则
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1533954 - 财政年份:2015
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Modeling the Optical Properties of Conjugated Polymer Assemblies: Interchain Vs. Intrachain Interactions
共轭聚合物组装体光学性质的建模:链间与链间的比较
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1203811 - 财政年份:2012
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$ 38.1万 - 项目类别:
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使用圆偏振光探测有机超分子组装体中的电子激发
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0906464 - 财政年份:2009
- 资助金额:
$ 38.1万 - 项目类别:
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Optical Excitations in Supramolecular Assemblies of Conjugated Oligomers and Polymers
共轭低聚物和聚合物超分子组装体中的光激发
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0606028 - 财政年份:2006
- 资助金额:
$ 38.1万 - 项目类别:
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Optical Excitations in Aggregates, Films and Crystals of Conjugated Oligomers and Polymers
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- 批准号:
0305173 - 财政年份:2003
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$ 38.1万 - 项目类别:
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Optical Excitations in Conjugated Oligomer and Polymer Aggregates: A Computational Approach
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0071802 - 财政年份:2000
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