Abstract
Photoexcitation of protonated aromatic amino acids leads to CαCβ bond breakage among other channels. There are two pathways for the CαCβ bond breakage, one is a slow process (microseconds) that occurs after hydrogen loss from the electronically excited ion, whereas the other is a fast process (nanoseconds). In this paper, a comparative study of the fragmentation of four molecules shows that the presence of the carboxylic acid group is necessary for this fast fragmentation channel to occur. We suggest a mechanism based on light-induced electron transfer from the aromatic ring to the carboxylic acid, followed by a fast internal proton transfer from the ammonium group to the negatively charged carboxylic acid group. The ion formed is a biradical since the aromatic ring is ionized and the carbon of the COOH group has an unpaired electron. Breakage of the weak CαCβ bond gives two even-electron fragments and is expected to quickly occur. The present experimental results together with the ab initio calculations support the interpretation previously proposed.
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