Minimally Empirical, First Principles-Derived Reactive Potential for Accelerated Simulations of Chemically Interacting Systems

在化学系化学理论、模型和计算方法（CTMC）项目的支持下，伊利诺伊大学厄巴纳-香槟分校的Alex Mironenko正在从第一性原理中开发最小经验反应原子间电位，以加速化学反应模拟和材料发现。在过去的100年里，量子化学方法的发展已经导致了新的分子、材料和在计算机上预测的反应，减少了昂贵的试错实验的数量。然而，这些方法仍然过于昂贵，无法描述化学转化的所有复杂性。数据驱动的近似方法——所谓的原子间势——更便宜，但往往忽略了基本的物理原理，并且需要大量昂贵的数据集才能达到准确性。米罗年科将利用20世纪60年代引入的一种被忽视的“化学伪势”理论，开发原子间势，以低成本整合所有所需的物理。他的研究小组将使用通用软件实现该方法，并评估其在对可再生能源具有重要意义的化学反应中的性能。更广泛地说，该技术旨在量化和统一化学反应性的基本概念，并将整合到本科生和研究生的教育模块中。这个项目将推广最小经验反应势，证明了最简单的氢团簇，主族元素包含s和p价轨道。将测试与该方法相关的几个假设和想法，包括但不限于：(1)电负性平衡，(2)有效原子伪势，以及(3)从基础量子理论推导的分析键序。该方法将使用通用的、可并行的开放获取软件来实现，旨在以较低的计算成本计算反应势能面。该方法将用于研究甲醛有机催化C-C偶联生成平台化学品- C3氧合物的机理。这种选择的动机是由于其影响和相对简单，可以将预测与最先进的从头算方法进行直接比较。如果成功，所提出的方法将为系统推导、最低经验和可转移的反应电位铺平道路，从而加速数据生成，进一步实现预测计算化学、催化和材料科学。这项研究也有可能创造关于基本的、教科书式的电子结构理论（哈克、分子轨道理论）的基本起源的新知识，总的来说，有可能为理论物理化学的描述/教学开辟新的途径。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。

With support from the Chemical Theory, Models, and Computational Methods (CTMC) program in the Division of Chemistry, Alex Mironenko of the University of Illinois at Urbana-Champaign is developing minimally empirical reactive interatomic potentials from first principles for accelerating chemical reaction simulations and materials discoveries. Quantum chemical methods being developed over the last 100 years have led to new molecules, materials, and reactions predicted on a computer, reducing the amount of costly trial-and-error experimentation. The methods, however, remain too expensive to describe all intricacies of chemical transformations. Data-driven approximate methods – so-called interatomic potentials – are more affordable but often miss essential physics and require large, expensive data sets for their accuracy. Mironenko will develop interatomic potentials that will incorporate all required physics at a low cost using an overlooked “chemical pseudo-potential” theory introduced in the 1960s. His research group will implement the method using general-purpose software and assess its performance on a chemical reaction of significance to renewable energy. More broadly, the technique aims to quantify and unify fundamental concepts of chemical reactivity and will be integrated into educational modules for both undergraduate and graduate students. This project will generalize the minimally empirical reactive potential, demonstrated for the simplest hydrogen clusters, to main-group elements containing s and p valence orbitals. Several hypotheses and ideas pertaining to the method will be tested, including, but not limited to (1) electronegativity equilibration, (2) effective atomic pseudo-potentials, and (3) analytical bond orders derived from the underlying quantum theory. The method will be implemented using general-purpose, parallelizable open-access software, designed to compute the reactive potential energy surface at a low computational cost. The method will be used to study the mechanism of organocatalytic C-C coupling of formaldehyde to form platform chemicals - C3 oxygenates. The choice is motivated by its impact and relative simplicity, enabling direct comparison of predictions with state-of-the-art ab initio methods. If successful, the proposed method will pave the way to systematically derived, minimally empirical, and transferable reactive potentials, thereby accelerating data generation and further enabling predictive computational chemistry, catalysis, and materials science. The research also has the potential to create new knowledge about the fundamental origins of elementary, textbook electronic structure theories (Huckel, molecular orbital theory), potentially opening up new approaches to the description/teaching of theoretical physical chemistry, in general.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.