Vuckovic Stefan, Gori-Giorgi Paola, Della Sala Fabio, Fabiano Eduardo
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, FEW , Vrije Universiteit , De Boelelaan 1083 , 1081HV Amsterdam , The Netherlands.
Institute for Microelectronics and Microsystems (CNR-IMM) , Via Monteroni, Campus Unisalento , 73100 Lecce , Italy.
J Phys Chem Lett. 2018 Jun 7;9(11):3137-3142. doi: 10.1021/acs.jpclett.8b01054. Epub 2018 May 29.
Approximate exchange-correlation functionals built by modeling in a nonlinear way the adiabatic connection (AC) integrand of density functional theory have many attractive features, being virtually parameter-free and satisfying different exact properties, but they also have a fundamental flaw: they violate the size-consistency condition, crucial to evaluate interaction energies of molecular systems. We show that size consistency in the AC-based functionals can be restored in a very simple way at no extra computational cost. Results on a large set of benchmark molecular interaction energies show that functionals based on the interaction strength interpolation approximations are significantly more accurate than second-order perturbation theory.
通过以非线性方式对密度泛函理论的绝热连接（AC）被积函数进行建模构建的近似交换关联泛函具有许多吸引人的特性，几乎无需参数且满足不同的精确性质，但它们也存在一个基本缺陷：它们违反了对评估分子系统相互作用能至关重要的尺寸一致性条件。我们表明，基于AC的泛函中的尺寸一致性可以以一种非常简单的方式恢复，且无需额外的计算成本。在大量基准分子相互作用能上的结果表明，基于相互作用强度插值近似的泛函比二阶微扰理论精确得多。
