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

基本信息

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

项目摘要

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.

在化学结构，动力学和机制A（CSDM-A）计划的支持下，亚利桑那大学的露西Ziurys和孟菲斯大学的Nathan Deyonker分别结合了实验和计算方法，以探索含有含有过渡金属的小分子的地面电子状态。过渡金属在催化和生物化学中起着重要作用，但是过渡金属和碳之间的化学键的基本特性仍然难以捉摸。即使使用现代，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合特性。 Ziurys和Deyonker团队将通过开发复杂的量子计算技术来准确预测含金属物质物种的分子特性，同时使用高分辨率的光谱测量来验证理论结果，以准确预测含金属物质物种的分子特性，从而促进过渡金属化学的理解。他们的发现可能会更好地了解未来清洁能源产生和存储应用中使用的催化剂，以及具有特殊聚合物或磁性特性的新材料的开发。研究生和本科级别的一群学生将参加该项目。他们将接受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。在4 GHz-850 GHz范围内将采用高分辨率，气相旋转光谱技术来研究金属碳化物和乙酰基物质中的化学键。感兴趣的金属包括Ni，Co，Ti和Fe。将使用毫米/亚MM直接吸收和傅立叶变换微波（FTMW）方法，并与发达的气相合成技术结合使用，旨在创建新型的反应性物种。实验工作将与涉及高阶，单个参考耦合群集和多方次配置相互作用理论的从头算计算同时进行。这种组合的方法将建立分子轨道，键类型，基态和低覆盖激发态，自旋轨道效应和静态电子相关的复杂歧管的组成。许多靶向物种都是开放式壳，涉及自旋轨道和自旋旋转耦合以及核自旋相互作用，因此在实验和计算上都在挑战。一个主要目标是提供适用于较大金属碳含有与许多化学领域有关的分子的预测理论电子和光谱特性，包括催化，合成，材料化学和化学生物学。该奖项反映了NSF的法定任务，并通过使用基础的智力效果和宽阔的范围来评估，并被视为值得通过评估的支持。

项目成果

期刊论文数量（2）

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

MgCCH (X 2 Î£ ) 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