Jump to main content
Jump to site search


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

Author affiliations

Abstract

Vibrational energy transfer in transition metal complexes with flexible structures 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. The central-metal effect on intramolecular vibrational energy redistribution (IVR) in M(CO)5Br was investigated in polar and nonpolar solvents. The linear infrared (IR) peak splitting between carbonyl vibrations increases as the metal atom changes from Mn to Re. The 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 the vibrational coupling strength between the two involved modes. In addition, the polar solvent is found to accelerate the IVR process by affecting the anharmonic vibrational potentials of a solute vibration mode.

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

Back to tab navigation

Supplementary files

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, Advance Article
  •   Request permissions

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

    F. Yang, X. Dong, M. Feng, J. Zhao and J. Wang, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C7CP05117D

Search articles by author

Spotlight

Advertisements