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、动力学和机理A(CSDM-A)计划的支持下，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化学键的基本性质仍然难以捉摸。即使使用现代高级计算机建模方法，即使是最简单的金属-碳键的化学键性质也很难预测。Ziurys和DeYonker团队将致力于通过开发复杂的量子计算技术来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，从而促进对过渡金属化学的理解。他们的发现可能会使人们更好地了解未来清洁能源发电和储存应用中使用的催化剂，以及具有特殊聚合物或磁性的新材料的开发。研究生和本科生的不同群体将参与该项目。他们将在现代实验和计算方法方面接受宝贵的培训，并全面参与科学发现过程。将在4 GHz-850 GHz范围内使用高分辨率的气相旋转光谱技术来研究金属碳化物和乙炔物种中的化学键。感兴趣的金属包括镍、钴、钛和铁。将使用毫米/亚毫米直接吸收和傅里叶变换微波(FTMW)方法，并结合旨在创造新的活性物种的成熟的气相合成技术。实验工作将与涉及高阶、单参考耦合团簇和多参考组态相互作用理论的从头计算相结合进行。这种结合的方法将建立分子轨道的组成、键类型、基态和低激发态的复杂流形、自旋-轨道效应和静态电子关联。许多目标物种是开壳层的，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。一个主要目标是提供适用于与许多化学领域相关的较大金属-碳分子的预测性理论、电子和光谱性质，包括催化、合成、材料化学和化学生物。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。

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