Infrared spectroscopy of jet-cooled neutral and ionized aniline-Ar

We report the infrared (IR) absorption spectrum of the jet-cooled neutral aniline–Ar Van der Waals complex together with that of the aniline–Ar cation in the 350–1700 cm−1 range. The spectra are measured using mass-selective ion detection in two different IR–ultraviolet double-resonance excitation schemes, using a free-electron laser as a source of widely tunable, intense IR radiation. A comparison with calculated IR spectra of the bare neutral aniline and of the cation of aniline allows for an unambiguous assignment of all the observed modes. The dissociation limit of the neutral aniline–Ar complex is bracketed between 273 and 329 cm−1, significantly lower than previously estimated. <br

The infrared spectrum of the benzene–Ar cation

The infrared (IR) absorption spectra of the jet-cooled C6H6 and C6D6 cations, complexed with Ar, are measured throughout the 450–1500 cm−1 region via IR-laser-induced vibrational dissociation spectroscopy. The IR spectrum of the C6H6–Ar cation is dominated by a Fermi resonance between the IR active v11 mode and two components of the combination mode of the lowest frequency modes v6 and v16 . A stringent upper limit of 316 cm−1 is found for the value of the dissociation limit D0 of the neutral C6D6–Ar complex

Gas-phase infrared spectra of cationized nitrogen-substituted polycyclic aromatic hydrocarbons

Gas-phase infrared spectra of several ionized nitrogen substituted polycyclic aromatic hydrocarbons (PANHs) have been recorded in the 600-1600 cm(-1) region via IR multiple-photon dissociation (IRMPD) spectroscopy. The UV photoionized PANH ions are trapped and isolated in a quadrupole ion trap where they are irradiated with an IR free electron laser. The PANHs were studied in their radical cation (PANH(+)) and protonated (H+ PANH) forms, and include quinoline, isoquinoline, phenanthridine, benzo[h] quinoline, acridine, and dibenzo[f,h] quinoline. Experimental IRMPD spectra were interpreted with the aid of density functional theory methods. The PANH(+) IR spectra are found to resemble those of their respective non-nitrogenated PAH cations. The IR spectra of H+ PANHs are significantly different owing to the NH inplane bending vibration, which generally couples very well with the aromatic CH bending and CC stretching modes. Implications of the NPAH (+, H+) laboratory spectra are discussed for the astrophysical IR emissions and, in particular, for the band at 6.2 mu m

Consequence of one-electron oxidation and one-electron reduction for aniline

Quantum-chemical calculations were performed for all possible isomers of neutral aniline and its redox forms, and intramolecular proton-transfer (prototropy) accompanied by π-electron delocalization was analyzed. One-electron oxidation (PhNH2 – e → [PhNH2]+•) has no important effect on tautomeric preferences. The enamine tautomer is preferred for oxidized aniline similarly as for the neutral molecule. Dramatical changes take place when proceeding from neutral to reduced aniline. One-electron reduction (PhNH2 + e → [PhNH2]-•) favors the imine tautomer. Independently on the state of oxidation, π- and n-electrons are more delocalized for the enamine than imine tautomers. The change of the tautomeric preferences for reduced aniline may partially explain the origin of the CH tautomers for reduced nucleobases (cytosine, adenine, and guanine)

Infrared spectroscopy of jet-cooled neutral and ionized aniline-ar

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The infrared spectrum of the benzene-ar cation

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