Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, Ontario M1C 1A4, Canada.
Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7, Canada.
J Chem Phys. 2017 Oct 28;147(16):164117. doi: 10.1063/1.5003825.
We suggest a non-iterative analytic method for constructing the exchange-correlation potential, v(r), of any singlet ground-state two-electron system. The method is based on a convenient formula for v(r) in terms of quantities determined only by the system's electronic wave function, exact or approximate, and is essentially different from the Kohn-Sham inversion technique. When applied to Gaussian-basis-set wave functions, the method yields finite-basis-set approximations to the corresponding basis-set-limit v(r), whereas the Kohn-Sham inversion produces physically inappropriate (oscillatory and divergent) potentials. The effectiveness of the procedure is demonstrated by computing accurate exchange-correlation potentials of several two-electron systems (helium isoelectronic series, H, H) using common ab initio methods and Gaussian basis sets.
我们提出了一种非迭代的解析方法，用于构建任何单重基态双电子系统的交换关联势 v(r)。该方法基于一个方便的公式，其中 v(r) 可以用仅由系统电子波函数（精确或近似的）确定的量来表示，与 Kohn-Sham 反演技术本质上不同。当应用于高斯基函数时，该方法给出了相应基组极限 v(r) 的有限基组近似，而 Kohn-Sham 反演则产生物理上不合适的（振荡和发散的）势。通过使用常见的从头算方法和高斯基组，计算了几个双电子系统（氦等电子系列、H、H）的精确交换关联势，证明了该方法的有效性。
