Vibrational dynamics of hydrogen-bonded HCl-diethyl ether complexes

We studied the relaxation of the H–Cl stretch vibration of hydrogen-bonded HCl-diethyl ether [HCl–(CH3CH2)2O] complexes at room temperature using femtosecond mid-infrared pump-probe spectroscopy. The lifetime of the H–Cl stretch vibration is determined to be 0.9±0.2 ps. The relaxation is found to oc...

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Bibliographic Details
Published in:The Journal of chemical physics 2000-03, Vol.112 (11), p.5127-5132
Main Authors: Giebels, I. A. M. E., van den Broek, M. A. F. H., Kropman, M. F., Bakker, H. J.
Format: Article
Language:English
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Summary:We studied the relaxation of the H–Cl stretch vibration of hydrogen-bonded HCl-diethyl ether [HCl–(CH3CH2)2O] complexes at room temperature using femtosecond mid-infrared pump-probe spectroscopy. The lifetime of the H–Cl stretch vibration is determined to be 0.9±0.2 ps. The relaxation is found to occur via an intermediate state which causes a transient blue-shift of the H–Cl stretch frequency. This blue-shift indicates that the low-frequency (CH3CH2)2O⋅⋅⋅H–Cl hydrogen bond is the main accepting mode of the vibrational energy. The excited population of this hydrogen-bond mode decays with a time constant of 3.1±0.5 ps to the ground state.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.481069