Comparison of ultrafast intense-field photodynamics in aniline and nitrobenzene: stability under amino and nitro substitution.

We report on the photoionization and photofragmentation of aniline (C6H5NH2) and nitrobenzene (C6H5NO2) under single-molecule conditions in the focus of 50 fs, 800 nm laser pulses. Ion mass spectra are recorded as a function of intensity ranging from 6 × 1012 to 3 × 1014 W cm-2. Ion yields are measured in the absence of the focal volume effect and without the need for additional deconvolution of data. We observe evidence of resonance-enhanced multiphoton ionization in aniline, in agreement with current literature. Phenyl-based ion fragments, singly-charged parent ions, and dissociative rearrangement processes are observed for both molecules. However, fragmentation in aniline is heavily suppressed in favor of parent ionization while the reverse is true for nitrobenzene, and multiply-charged parent ions are present in aniline and absent in nitrobenzene. We discuss the implications of these and other results as they relate to molecular stability against intense-field ionization and fragmentation, specifically with regards to the opposing behavior of the substituted amino and nitro functional groups.