Femtosecond probing of a 2c/3e disulfure bond making in liquid phase

Abstract : The subpicosecond ultraviolet observation of a sulfur−sulfur bond making (2σ/1σ* bond) is carried out in pure liquid dimethyl sulfide at 294 K. The early stages of a disulfide bonded radical formation (CH3SSCH3-) are characterized by a nonlinear λmax red shift of the absorption spectrum. In the temporal range 0−1600 fs, the red shift of 0.31 ± 0.1 eV is analyzed in the framework of a change of the 2σ/1σ* transition due to a lowering of the 2c,3e S−S bond strength and/or a destabilization of the σ lone pair during the demethylation process.
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Submitted on : Tuesday, March 15, 2011 - 12:41:21 PM
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Yann Gauduel, T. Launay, Abdeslem Hallou. Femtosecond probing of a 2c/3e disulfure bond making in liquid phase. Journal of Physical Chemistry A, American Chemical Society, 2002, 106 (9), pp.1727-1732. ⟨10.1021/jp0123684⟩. ⟨hal-00576762⟩

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