Abu-samha M, Børve K J
Department of Chemistry, University of Bergen, Bergen, Norway.
J Chem Phys. 2008 Apr 21;128(15):154710. doi: 10.1063/1.2904877.
We present a theoretical interpretation of the oxygen 1s photoelectron spectrum published by Ohrwall et al. [J. Chem. Phys. 123, 054310 (2005)]. A water cluster that contains 200 molecules was simulated at 215 K using the polarizable AMOEBA force field. The force field predicts longer O...O distances at the cluster surface than in the bulk. Comparisons to ab initio molecular dynamics (MD) simulations indicate that the force field underestimates the degree of surface relaxation. By comparing cluster lineshape models, computed from MD simulations, to the experimental spectrum we find further evidence of surface relaxation.
我们对Ohrwall等人发表的氧1s光电子能谱进行了理论解释[《化学物理杂志》123, 054310 (2005)]。使用可极化的AMOEBA力场在215 K下模拟了一个包含200个分子的水团簇。该力场预测团簇表面的O...O距离比团簇内部更长。与从头算分子动力学(MD)模拟的比较表明，该力场低估了表面弛豫程度。通过将MD模拟计算得到的团簇线形模型与实验光谱进行比较，我们发现了表面弛豫的进一步证据。
