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Updated: May 20, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Intramolecular Vibrational Energy Transfer in the Precatalyst [Mn(ppy)(CO)4] Tracked by Dual-Frequency 2D Infrared
Stefan Flesch1, Barbara Procacci1, Sabina Gurung1
1Department of Chemistry, The University of York, Heslington YO10 5DD, York, U.K.
This study reveals how energy moves within a metal carbonyl complex after light exposure. It shows energy transfers from the carbon monoxide ligand to the organic part and then to the solvent, crucial for understanding precatalyst activation.
Area of Science:
- * Inorganic Chemistry
- * Physical Chemistry
- * Spectroscopy
Background:
- * Thermal dissociation of carbon monoxide (CO) is key in metal carbonyl (MCO) catalytic cycles.
- * Understanding vibrational energy transfer is vital for precatalyst activation pathways.
- * Intramolecular vibrational energy redistribution (IVR) and intermolecular energy transfer (IET) influence MCO complex reactivity.
Purpose of the Study:
- * To investigate IVR in [Mn(ppy)(CO)4] using dual-frequency, 2D-IR spectroscopy.
- * To monitor energy transfer from CO ligands to the cyclometalated 2-phenylpyridine (ppy) ligand and solvent.
- * To elucidate the role of vibrational coupling in precatalyst activation.
Main Methods:
- * Dual-frequency, two-dimensional infrared (2D-IR) spectroscopy in dichloromethane solution.
- * Photoexcitation of carbonyl ligand stretching modes.
- * Monitoring vibrational modes of the ppy ligand.
- * Density functional theory (DFT) calculations.
Main Results:
- * Observed IVR from MCO to the ppy ligand within 35 ps.
- * Demonstrated IET to the solvent occurring within approximately 150 ps.
- * Identified distinct vibrationally excited states and uncommon negative anharmonic coupling.
- * Characterized time-dependent populations of low- and medium-frequency modes with specific rate constants for population and depopulation.
Conclusions:
- * Energy transfer dynamics in [Mn(ppy)(CO)4] are complex, involving IVR and IET.
- * Anharmonic coupling plays a significant role in spectral features and energy flow.
- * Findings provide insights into the activation mechanisms of metal carbonyl precatalysts.
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