Development of direct ab-initio dynamics method and its application to molecular designs

本文发展了处理反应动力学的直接从头算动力学方法，并将其应用于石墨表面的化学反应和离子、原子扩散动力学。在该方法中，反应体系的所有自由度都精确地包含在反应过程中。作为一个模型案例，我们用直接从头算动力学方法研究了水分子团簇的电离动力学。结果发现，离子化的水分子的质子在电离后200 fs内迅速转移到相邻的水分子。通过轨道计算研究了水分子团簇的电子俘获。过量电子首先被捕获在水分子团簇的表面态，然后水分子逐渐向过量电子方向移动，电子的ls-2 p跃迁随溶剂化时间发生蓝移.

Direct ab-initio dynamics method to treat reaction dynamics has been developed and applied to several chemical reactions and diffusion dynamics of ion and atoms on graphite surfaces. In this new method, all degrees of freedom of reaction system are precisely included during the reaction. As a model case, the ionization dynamics of water clusters have been investigated by means of direct ab-initio dynamics method. It was found that a proton of the ionized water molecule is rapidly transferred to the neighboring water molecule within 200 fs after the ionization. Electron capture of water clusters was also studied by the trajectory calculations. The excess electron was trapped firstly in the surface state of water cluster, and then the water molecules oriented gradually toward the excess electron. The ls-2p transition of electron was blue-shifted as a function of solvation time.