Staroverov Viktor N, Scuseria Gustavo E, Davidson Ernest R
Department of Chemistry, Rice University, Houston, Texas 77005, USA.
J Chem Phys. 2006 Apr 14;124(14):141103. doi: 10.1063/1.2194546.
It is commonly believed that the exchange-only optimized effective potential (OEP) method must yield total energies that are above corresponding ground-state Hartree-Fock (HF) energies except for one- and two-electron systems. We present a simple procedure for constructing local (multiplicative) exchange potentials that reproduce exactly the HF energy and density in any finite basis set for any number of electrons. For any finite basis set, no matter how large, there exist infinitely many such OEPs, which questions their suitability for practical applications.
人们普遍认为,仅交换优化有效势(OEP)方法得到的总能必定高于相应的基态哈特里 - 福克(HF)能,但单电子和双电子体系除外。我们提出了一种简单的程序来构建局域(乘法)交换势,该势在任意有限基组中对于任意数量的电子都能精确重现HF能量和密度。对于任何有限基组,无论其规模多大,都存在无穷多个这样的OEP,这对它们在实际应用中的适用性提出了质疑。