Manipulating coherent vibrational relaxation in ethylene carbonate with isotope substitution
Abstract
Two-dimensional infrared spectroscopy (2DIR) and linear IR spectroscopy investigate the behavior of coherent vibrational energy transfer between Fermi coupled vibrations in a series of ethylene carbonate (EC) 13C isotopologues. Analysis of the linear IR spectrum and the vibrational lifetimes of the Fermi doublet modes indicates that isotopic substitution strengthens the Fermi resonance condition while simultaneously suppressing population relaxation pathways involving a manifold of experimental dark states. The effects of this decoupling on the intrasystem relaxation of vibrational coherence states are investigated by Fourier analysis of 2DIR cross peaks and comparisons of the intensity of forbidden cross peaks in pump-selective 2DIR experiments. It is found that isotopic substitution also suppresses coherent relaxation pathways, indicating that coherent relaxation rates are governed by the effective coupling to the dark state manifold in a manner similar to population relaxation.
Article Details
Journal Info
The Journal of Chemical Physics
American Institute of Physics
Authors (5)
Luke Guerrieri
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA
Sarah Hall
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA
Carsten Mueller
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA
Brad M. Luther
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA
Amber T. Krummel
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA