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Central-metal effect on intramolecular vibrational energy transfer of M(CO)5Br (M = Mn, Re) probed by two-dimensional infrared spectroscopy

Abstract

Vibrational energy transfer in transition metal complexes with flexible structure in condensed phases is of central importance to catalytical chemistry processes. In this work, two molecules with different metal atoms, M(CO)5Br (where M = Mn, Re), were used as model systems, and their axial and radial carbonyl stretching modes as infrared probes. Central-metal effect on intramolecular vibrational energy redistribution (IVR) in M(CO)5Br was investigated in polar and nonpolar solvents. Linear infrared (IR) peak splitting between carbonyl vibrations increases as metal atom changes from Mn to Re. Waiting-time dependent two-dimensional infrared diagonal- and off-diagonal peak amplitudes reveal a faster IVR process in Re(CO)5Br than in Mn(CO)5Br. With the aid of density functional theory (DFT) calculations, the central-metal effect on IVR time linearly correlates with vibrational coupling strength between two involved modes. In addition, polar solvent is found to accelerate the IVR process by affecting the anharmonic vibrational potentials of a solute vibration mode.

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Publication details

The article was received on 28 Jul 2017, accepted on 22 Dec 2017 and first published on 02 Jan 2018


Article type: Paper
DOI: 10.1039/C7CP05117D
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    Central-metal effect on intramolecular vibrational energy transfer of M(CO)5Br (M = Mn, Re) probed by two-dimensional infrared spectroscopy

    F. Yang, Q. X. dong, M. Feng, J. zhao and J. Wang, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C7CP05117D

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