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Mixed IR/Vis Two‐Dimensional Spectroscopy: Chemical Exchange beyond the Vibrational Lifetime and Sub‐ensemble Selective Photochemistry
Author(s) -
van Wilderen Luuk J. G. W.,
Messmer Andreas T.,
Bredenbeck Jens
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201305950
Subject(s) - chemistry , spectroscopy , infrared spectroscopy , femtosecond , intermolecular force , excitation , spectral line , analytical chemistry (journal) , photochemistry , chemical physics , molecule , physics , laser , optics , organic chemistry , quantum mechanics , astronomy
Two‐dimensional exchange spectroscopy (2D EXSY) is a powerful method to study the interconversion (chemical exchange) of molecular species in equilibrium. This method has recently been realized in femtosecond 2D‐IR spectroscopy, dramatically increasing the time resolution. However, current implementations allow the EXSY signal (and therefore the chemical process of interest) only to be tracked during the lifetime ( T 1 ) of the observed spectroscopic transition. This is a severe limitation, as typical vibrational T 1 are only a few ps. An IR/Vis pulse sequence is presented that overcomes this limit and makes the EXSY signal independent of T 1 . The same pulse sequence allows to collect time‐resolved IR spectra after electronic excitation of a particular chemical species in a mixture of species with strongly overlapping UV/Vis spectra. Different photoreaction pathways and dynamics of coexisting isomers or of species involved in different intermolecular interactions can thus be revealed, even if the species cannot be isolated because they are in rapid equilibrium.