Structure, energetics and reaction dynamics vibrational spectra of gaseous ions

我们在气相离子化学的研究在下一个补助金期间的总体目标将是进一步推进的性质的理解间和分子内的相互作用中发现的不寻常的键合环境中经常显示的气相离子。这些目标将主要使用我们在滑铁卢实验室建造的四个新的实验装置来解决。这些构成三个高压质谱仪（HPMS）配置周围的单和双聚焦磁扇形质谱仪和傅立叶变换离子回旋共振（FTICR）光谱仪配备了高压离子分子团簇源。此外，在合作涉及自由电子激光（FEL）设施，克利奥，接口与FTICR光谱仪在巴黎大学南奥赛，我们将获得红外线光解光谱的新的集群离子，从而给出这些新的键合环境的振动签名上述。所有进行的实验研究都定期补充高层次的电子结构计算，这有助于获得结构和能量的洞察力。我们的注意力最近转向了从具有生物学意义的分子衍生的离子的化学。质子化氨基酸和小的碱性分子底物之间相互作用的能量学的氨基酸的初始HPMS研究已经揭示了这些相互作用可以导致氨基酸部分从中性到两性离子实体的转化的相对容易性。

The general objectives of our research in gas phase ion chemistry over the next grant period will be to further advance the understanding of the nature of inter- and intra-molecular interactions found in the unusual bonding environments frequently displayed by gas phase ions. These objectives will be addressed primarily using the four novel experimental apparatus that we have constructed in our laboratory at Waterloo. These constitute three high pressure mass spectrometers (HPMS) configured around both single and double focusing magnetic sector mass spectrometers and a Fourier Transform Ion Cyclotron Resonance (FTICR) spectrometer equipped with a high pressure ion-molecule cluster source. In addition, in a collaboration involving the Free Electron Laser (FEL) facility, CLIO, interfaced with a FTICR spectrometer at the University de Paris Sud-Orsay, we will obtain infra-red photodissociation spectra of novel cluster ions thus giving vibrational signatures of these novel bonding environments noted above. All of the experimental studies carried out are routinely complemented by high level electronic structure calculations which aid in gaining structural and energetic insight. Our attention has recently turned towards the chemistry of ions derived from molecules of biological significance. Initial HPMS studies of amino acids of the energetics of interaction between protonated amino acids and small, basic molecular substrates have revealed the relative ease with which these interactions can lead to the transformation of the amino acid moiety from a neutral to a zwitterionic entity.