Issue 1, 2014

Ionization-induced π → H site-switching in phenol–CH4 complexes studied using IR dip spectroscopy

Abstract

IR spectra of phenol–CH4 complexes generated in a supersonic expansion were measured before and after photoionization. The IR spectrum before ionization shows the free OH stretching vibration (νOH) and the structure of neutral phenol–CH4 in the electronic ground state (S0) is assigned to a π-bound geometry, in which the CH4 ligand is located above the phenol ring. The IR spectrum after ionization to the cationic ground state (D0) exhibits a red shifted νOH band assigned to a hydrogen-bonded cationic structure, in which the CH4 ligand binds to the phenolic OH group. In contrast to phenol–Ar/Kr, the observed ionization-induced π → H migration has unity yield for CH4. This difference is attributed to intracluster vibrational energy redistribution processes.

Graphical abstract: Ionization-induced π → H site-switching in phenol–CH4 complexes studied using IR dip spectroscopy

Article information

Article type
Paper
Submitted
20 Aug 2013
Accepted
22 Oct 2013
First published
13 Nov 2013

Phys. Chem. Chem. Phys., 2014,16, 110-116

Ionization-induced π → H site-switching in phenol–CH4 complexes studied using IR dip spectroscopy

M. Miyazaki, A. Takeda, M. Schmies, M. Sakai, K. Misawa, S. Ishiuchi, F. Michels, K. Müller-Dethlefs, O. Dopfer and M. Fujii, Phys. Chem. Chem. Phys., 2014, 16, 110 DOI: 10.1039/C3CP53533A

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