Liu Zhen-Fei, Burke Kieron
Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
J Chem Phys. 2009 Sep 28;131(12):124124. doi: 10.1063/1.3239472.
Modern density functional theory (DFT) calculations employ the Kohn-Sham system of noninteracting electrons as a reference, with all complications buried in the exchange-correlation energy (E(XC)). The adiabatic connection formula gives an exact expression for E(XC). We consider DFT calculations that instead employ a reference of strictly correlated electrons. We define a "decorrelation energy" that relates this reference to the real system, and derive the corresponding adiabatic connection formula. We illustrate this theory in three situations, namely, the uniform electron gas, Hooke's atom, and the stretched hydrogen molecule. The adiabatic connection for strictly correlated electrons provides an alternative perspective for understanding DFT and constructing approximate functionals.
现代密度泛函理论(DFT)计算采用非相互作用电子的Kohn-Sham体系作为参考,所有复杂因素都包含在交换关联能(E(XC))中。绝热连接公式给出了E(XC)的精确表达式。我们考虑采用严格关联电子作为参考的DFT计算。我们定义了一个将该参考与实际体系联系起来的“去关联能”,并推导了相应的绝热连接公式。我们在三种情况下阐述了该理论,即均匀电子气、胡克原子和拉伸的氢分子。严格关联电子的绝热连接为理解DFT和构建近似泛函提供了一个替代视角。