Glushkov Vitaly N, Fesenko Sergey I
Department of Physics, National University of Dnepropetrovsk, Dnepropetrovsk 49050, per Nauchny 13, Ukraine.
J Chem Phys. 2006 Dec 21;125(23):234111. doi: 10.1063/1.2403863.
In this paper the authors further develop and apply the direct-mapping density functional theory to calculations of the atomization energies and ionization potentials. Single-particle orbitals are determined by solving the Kohn-Sham [Phys. Rev. A. 140, 1133 (1965)] equations with a local effective potential expressed in terms of the external potential. A two-parametric form of the effective potential for molecules is proposed and equations for optimization of the parameters are derived using the exchange-only approximation. Orbital-dependent correlation functional is derived from the second-order perturbation theory in its Moller-Plesset-type zeroth-order approximation based on the Kohn-Sham orbitals and orbital energies. The total atomization energies and ionization potentials computed with the second-order perturbation theory were found to be in agreement with experimental values and benchmark results obtained with ab initio wave mechanics methods.
在本文中，作者进一步发展并应用直接映射密度泛函理论来计算原子化能和电离势。通过求解含以外部势表示的局域有效势的科恩 - 沈（《物理评论A》140, 1133 (1965)）方程来确定单粒子轨道。提出了分子有效势的双参数形式，并使用仅交换近似推导了参数优化方程。基于科恩 - 沈轨道和轨道能量，在其莫勒 - 普列塞特型零阶近似下，从二阶微扰理论导出轨道相关泛函。发现用二阶微扰理论计算的总原子化能和电离势与实验值以及用从头算波动力学方法获得的基准结果一致。
