Self-consistent Møller-Plesset Perturbation Theory For Excited States

Abstract

In quantum chemistry, obtaining a system's mean-field solution and incorporating electron correlation in a post Hartree-Fock (HF) manner comprise one of the standard protocols for ground-state calculations. In principle, this scheme can also describe excited states but is not widely used at present, primarily due to the difficulty of locating the mean-field excited states. With recent developments in excited-state orbital relaxation, self-consistent excited-state solutions can now be located routinely at various levels of theory. In this work, we explore the possibility of correcting HF excited states using Møller-Plesset perturbation theory to the second order. Among various PT2 variants, we find that the restricted open-shell MP2 (ROMP2) gives excitation energies comparable to the best density functional theory results, delivering $\sim 0.2$ eV mean unsigned error over a wide range of single-configuration state function excitations, at only non-iterative $O(N^5)$ computational scaling.

arXiv comment11 pages w/o references, 1 figure, 6 tables

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Cited by in corpus (2)

• Orbital Optimized Density Functional Theory for Electronic Excited States
• Third order Møller-Plesset theory made more useful? The role of density functional theory orbitals