Advancing Our Knowledge of the Transition Metal-Carbon Bond: Integrating Spectroscopy and Theory

增进我们对过渡金属-碳键的了解：光谱学和理论的结合

• 批准号: 2154121
• 负责人: Lucy Ziurys
• 金额: $ 52万
• 依托单位: University of Arizona
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-09-01 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154121&HistoricalAwards=false
• 关键词: Advancing; Our; Knowledge; Transition; Metal

With support from the Chemical Structure, Dynamics, and Mechanisms A (CSDM-A) program in the Division of Chemistry, Lucy Ziurys of the University of Arizona and Nathan DeYonker of University of Memphis, respectively, are combining experimental and computational methods to explore the ground electronic states of small molecules containing transition metals. Transition metals play a prominent role in catalysis and biochemistry, but the fundamental properties of chemical bonds between transition metals and carbon remains elusive. Even with modern-day, high-level computer modeling methods, it is difficult to predict the chemical bonding properties of the even simplest metal-carbon bonds. The Ziurys and DeYonker team will work to advance the understanding of transition metal chemistry through the development of sophisticated quantum computational techniques to accurately predict molecular properties of metal-containing species, while using high-resolution spectroscopic measurements to validate the theoretical results. Their discoveries could lead to a better understanding of catalysts used in future clean energy generation and storage applications, as well as the development of new materials with special polymeric or magnetic properties. A diverse group of students at the graduate and undergraduate levels will participate in the project. They will receive valuable training in modern experimental and computational methods and fully participate in the scientific discovery process.High-resolution, gas-phase rotational spectroscopy techniques will be employed in the 4 GHz-850 GHz range to investigate chemical bonding in metal carbide and acetylide species. Metals of interest include Ni, Co, Ti, and Fe. Both millimeter/sub-mm direct-absorption and Fourier transform microwave (FTMW) methods will be used, coupled with well-developed gas-phase synthetic techniques aimed at creating novel, reactive species. The experimental work will be carried out in tandem with ab initio calculations that involve higher-order, single reference coupled cluster and multireference configuration interaction theories. This combined approach will establish the composition of molecular orbitals, bond types, the ground state and the complex manifold of low-lying excited states, spin-orbit effects, and static electron correlations. Many of the targeted species are open-shell and involve spin-orbit and spin-spin couplings, as well as nuclear spin interactions, and thus are challenging both experimentally and computationally. A major goal is to provide predictive theoretical electronic and spectroscopic properties applicable to larger metal-carbon containing molecules relevant to many fields of chemistry, including catalysis, synthesis, materials chemistry, and chemical biology.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.

在化学系化学结构、动力学和机制A （CSDM-A）项目的支持下，亚利桑那大学的Lucy Ziurys和孟菲斯大学的Nathan DeYonker分别将实验和计算方法结合起来，探索含有过渡金属的小分子的基电子态。过渡金属在催化和生物化学中发挥着重要作用，但过渡金属与碳之间的化学键的基本性质仍然是难以捉摸的。即使使用现代的高级计算机建模方法，也很难预测最简单的金属-碳键的化学键性质。Ziurys和DeYonker团队将通过开发复杂的量子计算技术来提高对过渡金属化学的理解，以准确预测含金属物种的分子性质，同时使用高分辨率光谱测量来验证理论结果。他们的发现可能有助于更好地理解未来清洁能源生产和存储应用中使用的催化剂，以及开发具有特殊聚合物或磁性质的新材料。研究生和本科生的不同群体将参与该项目。他们将接受有关现代实验和计算方法的宝贵培训，并充分参与科学发现过程。高分辨率气相旋转光谱技术将在4ghz - 850ghz范围内用于研究金属碳化物和乙炔类物质的化学键合。感兴趣的金属包括Ni， Co， Ti和Fe。将使用毫米/亚毫米直接吸收和傅里叶变换微波（FTMW）方法，再加上发达的气相合成技术，旨在创造新的活性物质。实验工作将与从头计算一起进行，涉及高阶，单参考耦合簇和多参考配置相互作用理论。这种结合的方法将建立分子轨道的组成、键类型、基态和低洼激发态的复杂流形、自旋轨道效应和静态电子相关性。许多目标物质是开壳的，涉及自旋-轨道和自旋-自旋耦合，以及核自旋相互作用，因此在实验和计算上都具有挑战性。主要目标是提供预测的理论电子和光谱特性，适用于与许多化学领域相关的较大的含金属碳分子，包括催化、合成、材料化学和化学生物学。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。

项目成果

A computational and spectroscopic study of MgCCH (X 2 Σ + ): towards characterizing MgCCH +

MgCCH (X 2 Σ ) 的计算和光谱研究：表征 MgCCH

• DOI: 10.1080/00268976.2023.2267135
• 发表时间: 2023
• 期刊: Molecular Physics
• 影响因子: 1.7
• 作者: Burns, Joseph E.;Cheng, Qianyi;Fortenberry, Ryan C.;Sun, Ming;Zack, Lindsay N.;Zaveri, Trishal;DeYonker, Nathan J.;Ziurys, Lucy M.
• 通讯作者: Ziurys, Lucy M.

Neutral gas pressure dependence of ion–ion mutual neutralization rate constants using Landau–Zener theory coupled with trajectory simulations

使用朗道齐纳理论结合轨迹模拟计算离子与离子相互中和速率常数的中性气体压力依赖性

• DOI: 10.1063/5.0168609
• 发表时间: 2023
• 期刊: The Journal of Chemical Physics
• 作者: Liu, Zhibo;Roy, Mrittika;DeYonker, Nathan J.;Gopalakrishnan, Ranganathan
• 通讯作者: Gopalakrishnan, Ranganathan