Ayles Victoria L, Hammond Chris J, Bergeron Denis E, Richards Owen J, Wright Timothy G
School of Chemistry, University of Nottingham, Nottingham NG7 2RD, United Kingdom.
J Chem Phys. 2007 Jun 28;126(24):244304. doi: 10.1063/1.2741542.
Zero electron kinetic energy (ZEKE) spectroscopy is employed to gain information on the vibrational energy levels of the para-fluorotoluene (pFT) cation. Vibrationally resolved spectra are obtained following excitation through a range of intermediate vibrational energy levels in the S1 state. These spectra allow the observation of different cationic vibrational modes, whose assignment is achieved both from a knowledge of the S1 vibrational states and also by comparison with density functional calculations. In one notable case, clean ZEKE spectra were obtained from two overlapped S1 features. From the authors' data, the adiabatic ionization energy of pFT was derived as 70,946+/-4 cm(-1). The information on the cationic energy levels obtained will be useful in untangling the intramolecular vibrational redistribution dynamics of pFT in the S1 state.
零电子动能（ZEKE）光谱法被用于获取对氟甲苯（pFT）阳离子振动能级的信息。在通过S1态的一系列中间振动能级进行激发后，获得了振动分辨光谱。这些光谱使得能够观察到不同的阳离子振动模式，其归属可通过对S1振动态的了解以及与密度泛函计算的比较来实现。在一个显著的案例中，从两个重叠的S1特征中获得了清晰的ZEKE光谱。根据作者的数据，pFT的绝热电离能推导为70946±4 cm⁻¹。所获得的关于阳离子能级的信息将有助于理清pFT在S1态下的分子内振动再分布动力学。
