Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
J Chem Phys. 2011 Mar 7;134(9):094107. doi: 10.1063/1.3558739.
Electronically excited states of atoms and molecules in an environment may decay in interatomic processes by transferring excess energy to neighboring species and ionizing them. The corresponding interatomic decay width is the most important characteristic of the decay allowing to calculate its efficiency and the final states' distribution. In this paper we present calculations of interatomic widths by the Fano-Stieltjes method applied to Lanczos pseudospectra, which has been previously shown to provide accurate autoionization widths in atoms and molecules. The use of Lanczos pseudospectra allows one to avoid the full diagonalization bottleneck and makes the method applicable to larger systems. We apply the present method to the calculation of interatomic decay widths in NeMg, NeAr and HCN[middle dot]Mg(n), n = 1, 2 clusters. The results are compared with widths obtained analytically and by other ab initio methods where available.
在环境中，原子和分子的电子激发态可以通过将多余的能量传递给相邻的物种并使其离化来进行原子间过程衰变。相应的原子间衰变宽度是衰变的最重要特征，允许计算其效率和最终状态的分布。在本文中，我们通过应用于 Lanczos 伪谱的 Fano-Stieltjes 方法来计算原子间宽度，该方法先前已被证明可在原子和分子中提供准确的自电离宽度。Lanczos 伪谱的使用可以避免完全对角化的瓶颈，使该方法适用于更大的系统。我们将该方法应用于 NeMg、NeAr 和 HCN[中圆点]Mg(n)，n = 1，2 团簇中原子间衰变宽度的计算。将结果与可用的分析和其他从头算方法获得的宽度进行了比较。
