title: Two-Dimensional Infrared Study of (13)C-Natural Abundant Vibrational Transition Reveals Intramolecular Vibrational Redistribution Rather than Fluxional Exchange in Mn(CO)5Br.
abstract: In this work, molecular-symmetry enhanced (13)CO natural abundant isotopic infrared transition was identified in Mn(CO)5Br dissolved in CCl4 by FTIR spectroscopy. Diagonal and associated off-diagonal two-dimensional IR (2D IR) peaks of the (13)CO-species were found to be spectrally separated from the all-(12)CO species, allowing a direct probe of the (13)C natural abundant ensemble. Temperature-dependent FTIR experiment showed no evidence of ligand exchange in the metal carbonyl complex. Intramolecular vibrational redistribution dynamics among the CO stretching vibrational states were extracted using population-time dependent 2D IR diagonal and off-diagonal peaks for both radial mono-(13)CO and all-(12)CO isotopomers. This work demonstrates the potential use of natural abundant isotopic molecular species as a probe for revealing equilibrium and nonequilibrium structural dynamics in condensed-phase molecular systems.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, Institute of Chemistry, The Chinese Academy of Sciences , Beijing, 100190, People's Republic of China.
authors.forename: Fan
authors.initials: F
authors.lastname: Yang
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, Institute of Chemistry, The Chinese Academy of Sciences , Beijing, 100190, People's Republic of China.
authors.forename: Juan
authors.initials: J
authors.lastname: Zhao
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, Institute of Chemistry, The Chinese Academy of Sciences , Beijing, 100190, People's Republic of China.
authors.forename: Jianping
authors.initials: J
authors.lastname: Wang