Sandia National Laboratories, Albuquerque, New Mexico 87185, USA.
J Chem Phys. 2010 Oct 21;133(15):151102. doi: 10.1063/1.3505036.
Despite the fact that idempotent one-particle reduced density matrices are pervasive in quantum chemistry, the understanding of a general energy functional of such idempotent density matrices for the ground state energy has been lacking. By a constrained search, we show the structure of the general functional, illuminating the contributions from various terms. For the examples of the "best idempotent density matrix" and Kohn-Sham idempotent density matrices, we contrast the functional forms and suggest how the best idempotent density matrix approach may be a good starting point for further development.
尽管幂等单粒子约化密度矩阵在量子化学中普遍存在，但对于这种幂等密度矩阵的基态能量的一般能量泛函的理解一直缺乏。通过约束搜索，我们展示了一般泛函的结构，阐明了来自各个项的贡献。对于“最佳幂等密度矩阵”和 Kohn-Sham 幂等密度矩阵的例子，我们对比了函数形式，并提出了最佳幂等密度矩阵方法如何可能成为进一步发展的良好起点。
