Infrared photodissociation spectroscopy of [Aniline-(Water)n]+ (n = 1-8): Structural change from branched and cyclic to proton-transferred forms

TLDR: In this article, the infrared photodissociation spectra of [aniline−(H2O)n]- (n = 1−8) are measured in the 2700−3800 cm-1 region.

Abstract: Infrared photodissociation spectra of [aniline−(H2O)n]+ (n = 1−8) are measured in the 2700−3800 cm-1 region. The spectra are interpreted with the aid of density functional theory calculations. The n = 1 ion has an N−H···O hydrogen bond. The spectrum of the n = 2 ion demonstrates a large perturbation to both of the NH oscillators, indicating the 1−1 structure where each NH bond is bound to a water molecule. For the n = 3 ion, the calculated spectrum of the 2−1 branched structure coincides well with the observed one. For the n = 4 ion, there exist three strong bands at 2960, 3100, and 3430 cm-1, as well as a very weak one at 3550 cm-1. The observed spectrum in the 3600−3800 cm-1 region is decomposed into four bands centered at 3640, 3698, 3710, and 3734 cm-1. The 2−2 branched isomer is responsible for all the features except the 3550 and 3710 cm-1 bands. These two bands are due to another isomer with a five-membered ring. An infrared band characteristic of the n = 5 ion appears at 3684 cm-1, which is not se...