Vibrational and Structural Dynamics of Mn(CO)5Br and Re(CO)5Br Examined Using Nonlinear Infrared Spectroscopy |
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| Authors: | Min-jun Feng Fan Yang Jian-ping Wang |
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| Affiliation: | 1.Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;University of Chinese Academy of Sciences, Beijing 100049, China2.Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China |
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| Abstract: | Vibrational and structural dynamics of two transition metal carbonyl complexes, Mn(CO)5Br and Re(CO)5Br were examined in DMSO, using ultrafast infrared pump-probe spectroscopy, steady-state linear infrared spectroscopy and quantum chemistry computations. Two carbonyl stretching vibrational modes (a low-frequency A1 mode and two high-frequency degenerate E modes) were used as vibrational probes. Central metal effect on the CO bond order and force constant was responsible for a larger E-A1 frequency separation and a generally more red-shifted E and A1 peaks in the Re complex than in the Mn complex. A generally broader spectral width for the A1 mode than the E mode is believed to be partially due to vibrational lifetime effect. Vibrational mode-dependent diagonal anharmonicity was observed in transient infrared spectra, with a generally smaller anharmonicity found for the E mode in both the Mn and Re complexes. |
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| Keywords: | Transition metal carbonyl Transient IR spectroscopy Vibrational relaxation Anharmonicity |
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