ABSTRACT
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.
ABSTRACT
We report on the photoionization and photofragmentation of benzene (C(6)H(6)) and of the monohalobenzenes C(6)H(5)-X (X = F, Cl, Br, I) under intense-field, single-molecule conditions. We focus 50-fs, 804-nm pulses from a Ti:sapphire laser source, and record ion mass spectra as a function of intensity in the range â¼10(13) W/cm(2) to â¼10(15) W/cm(2). We count ions that were created in the central, most intense part of the focal area; ions from other regions are rejected. For all targets, stable parent ions (C(6)H(5)X(+)) are observed. Our data is consistent with resonance-enhanced multiphoton ionization (REMPI) involving the neutral (1)ππ* excited state (primarily a phenyl excitation): all of our plots of parent ion yield versus intensity display a kink when this excitation saturates. From the intensity dependence of the ion yield we infer that both the HOMO and the HOMO-1 contribute to ionization in C(6)H(5)F and C(6)H(5)Cl. The proportion of phenyl (C(6)H(5)) fragments in the mass spectra increases in the order X = F, Cl, Br, I. We ascribe these substituent-dependent observations to the different lifetimes of the C(6)H(5)X (1)ππ* states. In X = I the heavy-atom effect leads to ultrafast intersystem crossing to a dissociative (3)nσ* state. This breaks the C-I bond in an early stage of the ultrashort pulse, which explains the abundance of fragments that we find in the iodobenzene mass spectrum. For the lighter X = F, Cl, and Br this dissociation is much slower, which explains the lesser degree of fragmentation observed for these three molecules.
