화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.107, No.21, 4230-4237, 2003
Infrared photodissociation Spectroscopy of [aniline-(water)(n)](+) (n=1-8): Structural change from branched and cyclic to proton-transferred forms
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 = I 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 seen in the spectra of the n = 1-4 ions. This band is indicative of a ring structure and assigned to the free OH stretching vibration of the three-coordinated (double acceptor-single donor) H2O. The n = 5 ion has the five-membered ring structure with the fifth water molecule bound to the terminal (double acceptor) H2O. The observed spectra of the n = 6-8 ions show features quite different from those of the n = 1-5 ions; a very strong and broad band emerges around 3400 cm(-1), while no prominent bands appear below 3200 cm(-1). It is suggested that the n = 6-8 ions have proton-transferred structures.