Collaborative Research: Spectroscopic Studies of Metal-Containing Diatomics and Field Shift Effects

这笔来自化学结构、动力学和机制的赠款-A计划支持南伊利诺伊大学爱德华兹维尔的Leah O‘Brien教授和密苏里大学圣彼得堡分校的James O’Brien和Jack Harm教授的合作研究项目。路易。他们使用高分辨率电子光谱学来研究含有金属的小分子。这些研究有助于解释金属离子在形成化学键时被修饰的方式，为了解难以直接研究的较大金属分子的性质提供了有价值的见解。研究参与者通过一系列活动获得广泛的技能，包括开发仪器、使用光吸收和/或发射光谱方法收集数据以及数字数据分析。该项目继续了一个主要是本科院校和一所主要研究型大学的教职员工和学生之间的机构间合作。它加强了两所大学的研究基础设施，并培养学生和教师在当代光谱学和仪器开发方面的技能。该项目还包括一个外展计划，允许有天赋的高中生参与研究。奥布莱恩团队使用腔内激光吸收光谱和高分辨率傅里叶变换检测(ILS-FTS)相结合。产生感兴趣的分子的等离子体放电技术使用工业中使用的直流(DC)和射频(RF)脉冲直流等离子体发生器。对光谱进行旋转分析以获得新的和/或改进的分子常数(例如，具有多个同位素的物种的跃迁能、转动和振动常数、角动量耦合常数、与质量无关的参数)。这些常数被用来绘制分子的能级图和势能曲线，甚至可以通过电场移动效应一瞥金属核，这是最近针对含铂分子的特征。这些参数可以将实验结果与同事邹文丽教授正在进行的这些小分子的高级计算结果进行比较。这项工作加深了我们对金属-配体相互作用、金属-配体结合的周期性趋势的理解，并提供了对金属催化反应的洞察。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。

This grant from the Chemical Structure, Dynamics, and Mechanisms-A program supports the collaborative research projects of Professor Leah O’Brien at Southern Illinois University Edwardsville and Professors James O’Brien and Jack Harms at the University of Missouri-St. Louis. They use high-resolution electronic spectroscopy to investigate small, metal-containing molecules. These studies help to explain the way that metal ions are modified when they form chemical bonds, providing valuable insight into the nature of larger metal-containing molecules that are difficult to study directly. Research participants acquire a wide range of skills through a combination of activities, including development of instrumentation, data collection using light-absorption and/or emission spectroscopic methods, and digital data analysis. This project continues an inter-institutional collaboration of faculty and students at a primarily undergraduate institution and a major research university. It enhances the research infrastructure at both universities and develops students and faculty with skills in contemporary spectroscopy and instrument development. The project also contains an outreach program that allows talented high school students to participate in the research.The O'Brien groups use intracavity laser absorption spectroscopy combined with high resolution Fourier transform detection (ILS-FTS). The plasma discharge techniques to produce the molecules of interest employ direct current (DC) and radio frequency (RF) pulsed DC plasma generators as used in industry. The spectra are rotationally analyzed to obtain new and/or improved molecular constants (e.g., transition energy, rotational and vibrational constants, angular momentum coupling constants, mass-independent parameters for species with multiple isotopologues). These constants are used to develop energy level diagrams and potential energy curves for molecules and may even provide a glimpse of the metal nucleus through the electronic field-shift effect, which was recently characterized for platinum-containing molecules. These parameters enable comparison of the experimental results with on-going, high-level computational results from colleague Prof. Wenli Zou for these small molecules. This work enhances our understanding of metal-ligand interactions, periodic trends for metal-ligand binding, and provides insight on metal-catalyzed reactions.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.