Self-interaction corrected density functional calculations of molecular Rydberg states
Self-interaction corrected density functional calculations of molecular Rydberg states
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DOI：
10.1063/1.4829539
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发表时间：
2013-11-21
影响因子：
4.4
通讯作者：
Jonsson, Hannes
中科院分区：
文献类型：
--
作者：
Gudmundsdottir, Hildur;Zhang, Yao;Jonsson, Hannes
提出了一种计算分子里德伯激发态的波函数和能量的方法。使用基态密度泛函理论（包括 Perdew-Zunger 自相互作用校正和优化的有效势）可以获得对里德堡态轨道的良好估计。激发分子的总能量是使用 Delta 自洽场方法获得的，其中电子从最高占据轨道移出并置于里德伯轨道中。显示了 NH3、H2O、H2CO、C2H4 和 N(CH3)(3) 的前几个里德伯态的结果。这里给出的 33 个分子里德伯态能量的平均绝对误差是 0.18 eV。轨道在真实的空间网格上表示，避免了对扩散原子基组的依赖。与标准密度泛函理论计算一样，计算量为 NM2，其中 N 是轨道数量，M 是计算中包含的网格点数量。由于计算工作随系统尺寸的缓慢扩展以及真实空间网格方法中的高并行性，这里提出的方法使得估计大分子中的里德伯电子结合能成为可能。 (C) 2013 AIP 出版有限责任公司。
A method is presented for calculating the wave function and energy of Rydberg excited states of molecules. A good estimate of the Rydberg state orbital is obtained using ground state density functional theory including Perdew-Zunger self-interaction correction and an optimized effective potential. The total energy of the excited molecule is obtained using the Delta Self-Consistent Field method where an electron is removed from the highest occupied orbital and placed in the Rydberg orbital. Results are presented for the first few Rydberg states of NH3, H2O, H2CO, C2H4, and N(CH3)(3). The mean absolute error in the energy of the 33 molecular Rydberg states presented here is 0.18 eV. The orbitals are represented on a real space grid, avoiding the dependence on diffuse atomic basis sets. As in standard density functional theory calculations, the computational effort scales as NM2 where N is the number of orbitals and M is the number of grid points included in the calculation. Due to the slow scaling of the computational effort with system size and the high level of parallelism in the real space grid approach, the method presented here makes it possible to estimate Rydberg electron binding energy in large molecules. (C) 2013 AIP Publishing LLC.