Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, USA.
J Am Soc Mass Spectrom. 2010 May;21(5):681-93. doi: 10.1016/j.jasms.2010.01.028. Epub 2010 Feb 1.
The ASMS conference on ion spectroscopy brought together at Asilomar on October 16-20, 2009 a large group of mass spectrometrists working in the area of ion spectroscopy. In this introduction to the field, we provide a brief history, its current state, and where it is going. Ion spectroscopy of intermediate size molecules began with photoelectron spectroscopy in the 1960s, while electronic spectroscopy of ions using the photodissociation "action spectroscopic" mode became active in the next decade. These approaches remained for many years the main source of information about ionization energies, electronic states, and electronic transitions of ions. In recent years, high-resolution laser techniques coupled with pulsed field ionization and sample cooling in molecular beams have provided high precision ionization energies and vibrational frequencies of small to intermediate sized molecules, including a number of radicals. More recently, optical parametric oscillator (OPO) IR lasers and free electron lasers have been developed and employed to record the IR spectra of molecular ions in either molecular beams or ion traps. These results, in combination with theoretical ab initio molecular orbital (MO) methods, are providing unprecedented structural and energetic information about gas-phase ions.
2009 年 10 月 16 日至 20 日，ASMS 会议在阿西洛马召开，聚集了一大批从事离子光谱学领域工作的质谱学家。在这个领域的介绍中，我们提供了一个简短的历史、当前的状态和未来的发展方向。中等大小分子的离子光谱学始于 20 世纪 60 年代的光电电子能谱，而在接下来的十年中，使用光解“作用光谱”模式的离子电子光谱学变得活跃起来。这些方法多年来一直是关于离子电离能、电子态和电子跃迁的主要信息来源。近年来，高分辨率激光技术与分子束中的脉冲场电离和样品冷却相结合，为包括自由基在内的中小分子提供了高精度的电离能和振动频率。最近，光学参量振荡器（OPO）IR 激光和自由电子激光已经被开发并应用于记录分子离子在分子束或离子阱中的红外光谱。这些结果与从头算分子轨道（MO）理论方法相结合，为气相离子提供了前所未有的结构和能量信息。
