An accurate relativistic effective core potential for excited states of Ag atom:: An application for studying the absorption spectra of Agn and Agn+ clusters
An accurate relativistic effective core potential for excited states of Ag atom:: An application for studying the absorption spectra of Agn and Agn+ clusters
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DOI：
10.1063/1.478242
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发表时间：
1999-02-22
影响因子：
4.4
通讯作者：
Fantucci, P
中科院分区：
文献类型：
--
作者：
Bonacic-Koutecky, V;Pittner, J;Fantucci, P
基于相关理论水平和相关原子轨道（AO）基组，导出了一种新的银原子 11 电子相对论有效核心势（11e-RECP），可以准确确定激发态。通过将计算的二聚体激发态与实验数据进行比较，这一点得到了验证。因此，我们在线性响应运动方程耦合团簇（EOM-CC）方法的框架中应用新的11e-RECP来确定小Agn=2-4和Ag-n=2-4(+)团簇的吸收光谱。每个原子 11 个电子的相关处理以及大能量区间内跃迁能量和振荡器强度的计算使我们能够研究 d 电子对光谱图案的影响。我们发现，d 电子对于吸收光谱的准确预测起着至关重要的作用，尽管它们并不总是直接参与导致强烈跃迁的主要激发。将计算出的稳定结构的光谱图案与可用的实验数据进行比较。 (C) 1999 年美国物理研究所。 [S0021-9606(99)30306-8]。
A new 11-electron relativistic effective core potential (11e-RECP) for Ag atom based on correlated level of theory and the associated atomic orbital (AO) basis set have been derived which allows for an accurate determination of excited states. This has been verified by comparing the calculated excited states of the dimer with experimental data. Therefore, we applied the new 11e-RECP in the framework of the linear response equation-of-motion coupled-cluster (EOM-CC) method to determine absorption spectra of small Agn=2-4 and Ag-n=2-4(+) clusters. The correlation treatment of 11 electrons per atom and calculations of transition energies and oscillator strengths in a large energy interval allowed us to investigate the influence of d-electrons on the spectroscopic patterns. We have found that d-electrons play a crucial role for accurate predictions of absorption spectra in spite of the fact that they are not always directly involved in the leading excitations contributing to the intense transitions. The calculated spectroscopic patterns for the stable structures are compared with available experimental data. (C) 1999 American Institute of Physics. [S0021-9606(99)30306-8].