Spectroscopy of Multiply-Charged Transition Metal Ions Clustered with Solvent

范德比尔特大学的琳玛丽·波西得到了实验研究的支持， 物理化学计划，研究气相光谱的 双电荷过渡金属（TM）离子与溶剂成簇。 配位的双电荷TM离子在凝聚态中是很常见的， 相，但不是在气相中，因为第二电离电位 (IP)金属的量大于配体IP，并且金属离子排斥 得到的阳性配体。 电喷雾离子化（ESI） 用于将聚集的二价离子从凝聚态转移到 气相，不还原金属。 她将联合收割机ESI和 激光光谱学研究（a）电子吸收光谱学 中性溶剂，以评估电子或结构扰动 由配位或静电结合产生;（B） 最低能量配体-金属电荷转移带作为 溶剂分子数;（c）d-d跃迁。 系统被 研究了第一排TM离子与各种中性溶剂的团簇 分子的碱性、极性、空间体积和 振动结构 大多数涉及过渡金属的有趣的化学反应发生在 凝聚相，但分析工具提供了最精确的 信息通常是气相技术。 很明显， 必须保证气相系统和凝相系统 尽可能相似。 电喷雾电离技术将允许 将化学上感兴趣的溶液相物质转移到气体中 高分辨率激光光谱学可以用于 提供了关于二价的结构的非常详细的信息， 过渡金属离子

Lynmarie Posey of Vanderbilt University is supported by the Experimental Physical Chemistry Program to study the gas-phase spectroscopy of doubly-charged transition metal (TM) ions clustered with solvent. Coordinated doubly-charged TM ions are quite common in the condensed phase, but not in the gas phase, since the second ionization potential (IP) of the metal is greater than the ligand IP, and the metal ion repels the resulting positive ligand. Electrospray ionization (ESI) has been used to transfer the clustered doubly-valent ion from the condensed to the gas phase, without reduction of the metal. She will combine ESI and laser spectroscopy to study (a) the electronic absorption spectroscopy of the neutral solvent to assess the electronic or structural perturbations resulting from coordination or electrostatic binding; (b) change in the lowest energy ligand-to-metal charge transfer band as a function of the number of solvent molecules; (c) d-d transitions. Systems to be investigated are first row TM ions clustered with various neutral solvent molecules which differ in their basicity, polarity, steric bulk and vibrational structure. Most of the interesting chemistry involving transition metals occurs in the condensed phase yet the analytical tools providing the most precise information are often gas-phase techniques. It is clear then that one must ensure that the gas-phase system and condensed phase system are as similar as possible. The electrospray ionization technique will allow transfer of the chemically interesting solution phase species to the gas phase where high resolution laser spectroscopy can be brought to bear to provide extremely detailed information on the structure of the divalent transition metal ions.