Grégoire Gilles, Jouvet Christophe, Dedonder Claude, Sobolewski Andrzej L
Laboratoire de Physique des Lasers du CNRS, Institut Galilée, Université Paris 13, 93430 Villetaneuse, France.
J Am Chem Soc. 2007 May 16;129(19):6223-31. doi: 10.1021/ja069050f. Epub 2007 Apr 21.
In recent experiments, the excited-state lifetimes of protonated aromatic amino acids (TrpH+ and TyrH+) have been recorded by means of pump-probe photodissociation technique. The lifetime of TyrH+ is much longer than that of TrpH+, which has been initially rationalized on the basis of a simple phenomenological model. Besides, specific photofragments including the formation of radical cation after hydrogen loss are observed for TrpH+ that are not found for TyrH+. The ab initio calculations reported here for TrpH+ and TyrH+ using a coupled-cluster method are meant to track the rich photochemistry of these protonated amino acids following UV excitation.
在最近的实验中，通过泵浦 - 探测光解离技术记录了质子化芳香族氨基酸（TrpH⁺和TyrH⁺）的激发态寿命。TyrH⁺的寿命比TrpH⁺长得多，这最初是基于一个简单的唯象模型进行解释的。此外，观察到TrpH⁺会产生特定的光碎片，包括氢损失后形成的自由基阳离子，而TyrH⁺则未观察到这些。本文使用耦合簇方法对TrpH⁺和TyrH⁺进行的从头算计算旨在追踪这些质子化氨基酸在紫外激发后的丰富光化学过程。
