Polaritonic Quantum Chemistry

佛罗里达州立大学的尤金·德普林斯得到了化学系化学理论、模型和计算方法项目的支持，该项目旨在开发描述强耦合轻物质系统的理论工具。纳米受限光子和分子系统之间的强烈相互作用可能会导致混合光物质状态的产生，即所谓的极化激子，它可能会显示出与其母成分非常不同的化学和物理性质。这些极化子态在技术和化学上的应用是广泛的。最近的基于腔的催化、极化激元激光和基于等离子体的光稳定的例子只提供了对极化激子方法在化学和材料科学中的变革潜力的一瞥。为了使该领域完全兑现其承诺，超强光-物质耦合的实验实现必须伴随着对极化子特性的高质量理论描述。德普林斯小组将为极化子结构的从头计算描述开发一个健壮、可靠和可系统改进的框架。即将开发的理论和软件将填补现有计算工具包中用于高精度描述极化介子过程的空白。这些工具有可能促进基于极化的新技术的合理设计，这些技术与光收集、超导和量子信息科学相关。所有在该计划下开发的软件都将以免费和开源的方式发布。根据这一奖项，德普林斯小组还将为量子化学和计算机科学教育开发易于获取的在线教育材料。德普林斯博士和他的团队将采用多体方法来解决极化子结构问题，重点是运动方程(EOM)耦合团簇(CC)方法层次。激发能(EE)、电离势(IP)和电子亲和能(EA)的极化子公式EOM-CC理论和软件将被发展并应用于涉及空穴束缚分子的各种问题。从头算对强和超强轻物质耦合的描述很少见，最近出现了几个现有的多体方法来解决这个问题的例子。鉴于密度泛函理论(DFT)中极化子公式中电子-光子交换-关联泛函的确切形式尚不清楚，在该计划下将开发的多体方法，如EOM-CC方法，似乎提供了对腔-分子相互作用的普遍可靠和系统改进的描述的唯一途径。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

Eugene DePrince of Florida State University is supported by an award from the Chemical Theory, Models and Computational Methods program in the Division of Chemistry to develop theoretical tools for the description of strongly-coupled light-matter systems. Strong interactions between nanoconfined photons and molecular systems can lead to the creation of hybrid light-matter states, known as polaritons, that may display remarkably different chemical and physical properties than their parent components. The technological and chemical applications of these polariton states are wide-ranging. Recent examples of cavity-based catalysis, polariton lasing, and plasmon-based photostabilization offer only a glimpse into the transformative potential of polaritonic approaches to chemistry and materials science. In order for the field to fully live up to its promise, the experimental realization of ultra-strong light-matter coupling must be accompanied by high-quality theoretical descriptions of the properties of polaritonic features. The DePrince group will develop a robust, reliable, and systematically improvable framework for the ab initio description of polaritonic structure. The theories and software that will be developed will fill a gap in the existing computational tool kit for the high-accuracy description of polariton-mediated processes. Such tools have the potential to facilitate the rational design of new polariton-based technologies relevant to light harvesting, super conductivity, and quantum information science. All software developed under this program will be released in a free and open-source manner. Under this award, the DePrince group also will be developing readily accessible online educational materials for quantum chemistry and computer science education. Dr. DePrince and his team will take a many-body approach to the polaritonic structure problem, with an emphasis on the equation-of-motion (EOM) coupled-cluster (CC) hierarchy of methods. Polaritonic formulations of excitation-energy (EE), ionization potential (IP), and electron affinity (EA) EOM-CC theory and software will be developed and applied to a variety of problems involving cavity-bound molecules. Ab initio descriptions of strong and ultra-strong light-matter coupling are rare, with only a few existing examples of many-body approaches to this problem having recently emerged. Given that the exact form of the electron-photon exchange-correlation functional in polaritonic formulations of density functional theory (DFT) is unknown, it appears that many-body methods such as the EOM-CC approaches that will be developed under this program offer the only route to universally reliable and systematically improvable descriptions of cavity-molecule interactions.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.