Accurate excitation energies from time-dependent density functional theory: Assessing the PBE0 model
Accurate excitation energies from time-dependent density functional theory: Assessing the PBE0 model
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DOI：
10.1063/1.479571
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发表时间：
1999-08-15
影响因子：
4.4
通讯作者：
Barone, V
中科院分区：
文献类型：
--
作者：
Adamo, C;Scuseria, GE;Barone, V
我们分析的性能，通过结合Perdew-Burke-Erzenrhof（PBE）广义梯度泛函与预定量的精确交换预测垂直电子激发能内的时间依赖性的方法得到的密度泛函模型。四个分子，即CO，H_2CO，（CH_3）（_2）CO，和C_2H_4已被选为基准情况。我们的结果表明，该模型（PBE 0）提供了准确的激发价和里德伯态。此外，结果在数值上接近使用渐近正确的交换相关泛函。PBE 0模型预测激发能在较大的分子的性能进行评估苯，吡啶，萘。在这里，PBE 0模型提供的结果是相当好的协议与实验数据和类似的质量，通过更复杂的（和耗时的）后Hartree-Fock方法获得的。(C)1999年美国物理学会。[S0021-9606（99）30531-6]。
We analyze the performance of a density functional model obtained by combining the Perdew-Burke-Erzenrhof (PBE) generalized gradient functional with a predetermined amount of exact exchange for predicting vertical electronic excitation energies within a time-dependent approach. Four molecules, namely, CO, H2CO, (CH3)(2)CO, and C2H4, have been chosen as benchmark cases. Our results show that this model (PBE0) provides accurate excitations both to valence and Rydberg states. Furthermore, the results are numerically close to those obtained using asymptotically correct exchange-correlation functionals. The performance of the PBE0 model for predicting excitation energies in larger molecules is assessed for benzene, pyridine, and naphthalene. Here, the PBE0 model provides results which are in fairly good agreement with experimental data and of similar quality to those obtained by more sophisticated (and time-consuming) post-Hartree-Fock methods. (C) 1999 American Institute of Physics. [S0021-9606(99)30531-6].