Structure, Energetics, Reaction Dynamics and Vibrational Spectra of Gaseous Ions

我们的研究在下一个补助金期间的总体目标将是扩大的理解，发现在新的键合环境中的分子间和分子内的相互作用经常显示气相离子和探测气相离子的单分子和双分子反应动力学的性质。为了解决这些目标，我们将使用一个四管齐下的方法结合实验和计算研究。第一种实验方法是高压质谱法（HPMS），它允许研究气相离子分子反应和平衡作为温度的函数。通过这种方式，可以获得这些过程的ΔHo和ΔSo的准确实验值，从而对所涉及的势能景观有准确、定量的理解。第二种实验方法涉及傅里叶变换离子回旋共振光谱法（FTICR），它允许在低压下将离子限制在电磁阱中很长一段时间。第三种技术是红外多光子解离（IRMPD）实验，涉及自由电子激光（FEL）。最后，我们所有的实验工作都伴随着使用电子结构方法的计算研究，这大大有助于理解键合和能量学以及振动光谱的解释。

The general objectives of our research over the next grant period will be to expand the understanding of the nature of inter- and intra-molecular interactions found in the novel bonding environments frequently displayed by gas phase ions and to probe both the unimolecular and bimolecular reaction dynamics of gas phase ions. In order to address these objectives we will use a four-pronged approach combining both experimental and computational studies. The first of the experimental methods used is High Pressure Mass Spectrometry (HPMS), which permits the study of gas-phase ion-molecule reactions and equilibria as a function of temperature. In this way, accurate experimental values of ΔHo and ΔSo can be obtained for these processes leading to an accurate, quantitative understanding of the potential energy landscapes involved. The second experimental approach involves Fourier Transform Ion Cyclotron Resonance Spectrometry (FTICR) which permits confinement of ions in an electromagnetic trap for extremely long periods of time at low pressures. The third technique exploited is Infrared Multiple Photon Dissociation (IRMPD) experiments involving a Free Electron Laser (FEL). Finally, all of our experimental work is accompanied by computational studies using electronic structure methods which greatly aid in the understanding of bonding and energetics as well as in the interpretation of vibrational spectra.