Laboratoire de Chimie et de Physique Quantiques, IRSAMC, CNRS and Université de Toulouse, 118 route de Narbonne, 31062, Toulouse Cedex, France.
J Phys Chem A. 2010 Mar 11;114(9):3287-96. doi: 10.1021/jp909443p.
Relaxation dynamics following photoexcitation of a calcium atom deposited on an icosahedral-like argon cluster Ar(n) (n approximately = 55) is investigated through theoretical simulations. Based on ab initio calculations of the CaAr molecule, a diatomics-in-molecules model is set up to efficiently describe the electronic excited states of the system. The excited state dynamics is studied using molecular dynamics with electronic transitions (Tully, J. C. J. Chem. Phys. 1990, 93, 1061). The signature of this dynamics in the time-resolved photoelectron spectra is investigated, to assess the possibility of detecting competing vibrational and electronic relaxations through pump-probe experiments. The vibrational relaxation, influenced by nonadiabatic transitions, can clearly be seen in the time-resolved photoelectron spectra. The details of the electronic relaxation, as well as the possible ejection of the chromophore, are found to be sensitive to the local environment of the calcium atom deposited on the argon cluster.
通过理论模拟研究了钙原子沉积在类二十面体氩团簇 Ar(n)（n 约为 55）上后光激发的弛豫动力学。基于 CaAr 分子的从头算计算，建立了双原子分子模型以有效地描述系统的电子激发态。使用分子动力学与电子跃迁（Tully，J. C. J. Chem. Phys. 1990, 93, 1061）研究了激发态动力学。研究了时间分辨光电子能谱中这种动力学的特征，以评估通过泵浦探测实验检测竞争振动和电子弛豫的可能性。受非绝热跃迁影响的振动弛豫在时间分辨光电子能谱中清晰可见。电子弛豫的细节，以及发色团的可能发射，被发现对沉积在氩团簇上的钙原子的局部环境敏感。
