Department of Chemistry, University of California, Berkeley, California 94720, USA.
J Chem Phys. 2018 Aug 28;149(8):081101. doi: 10.1063/1.5045056.
We present a mean field theory for excited states that is broadly analogous to ground state Hartree-Fock theory. Like Hartree-Fock, our approach is deterministic, state-specific, applies a variational principle to a minimally correlated ansatz, produces energy stationary points, relaxes the orbital basis, has a Fock-build cost-scaling, and can serve as the foundation for correlation methods such as perturbation theory and coupled cluster theory. To emphasize this last point, we pair our mean field approach with an excited state analog of second order Møller-Plesset theory and demonstrate that in water, formaldehyde, neon, and stretched lithium fluoride, the resulting accuracy far exceeds that of configuration interaction singles and rivals that of equation of motion coupled cluster.
我们提出了一种激发态的平均场理论,它与基态 Hartree-Fock 理论大致类似。与 Hartree-Fock 理论一样,我们的方法是确定性的、特定于状态的,它将变分原理应用于最小相关的假设,产生能量稳定点,放松轨道基,具有 Fock 构建成本缩放,并可以作为诸如微扰理论和耦合簇理论等相关方法的基础。为了强调最后一点,我们将我们的平均场方法与二阶 Møller-Plesset 理论的激发态类似物配对,并证明在水中、甲醛、氖和拉伸的氟化锂中,所得的准确性远远超过组态相互作用单电子的准确性,并且可以与运动方程耦合簇相媲美。