RPA natural orbitals and their application to post-Hartree-Fock electronic structure methods

Abstract

We present a method to approximate post-Hartree-Fock correlation energies by using approximate natural orbitals obtained by the random phase approximation (RPA). We demonstrate the method by applying it to the helium atom, the hydrogen and fluorine molecule, and to diamond as an example of a periodic system. For these benchmark systems, we show that RPA natural orbitals converge the MP2 correlation energy rapidly. Additionally, we calculated full configuration interaction energies for He and H${}_2$, which are in excellent agreement with the literature and experimental values. We conclude that the proposed method may serve as a compromise to reach good approximations to correlation energies at moderate computational cost, and we expect the method to be especially useful for theoretical studies on surface chemistry by providing an efficient basis to correlated wave function based methods.

arXiv comment10 pages, 18 figures, 16 Equations; v2: fixed typo in metadata abstract, changed bibliography style; v3: added reference (4), added Acknowledgement

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Cited by in corpus (11)

• Local embedding of Coupled Cluster theory into the Random Phase Approximation using plane-waves
• Surface science using coupled cluster theory via local Wannier functions and in-RPA-embedding: the case of water on graphitic carbon nitride
• Accelerating the Convergence of Auxiliary-Field Quantum Monte Carlo inSolids with Optimized Gaussian Basis Sets
• Optimized effective potentials from the random-phase approximation: Accuracy of the quasiparticle approximation
• Quantum Computation for Predicting Electron and Phonon Properties of Solids
• Phaseless auxiliary field quantum Monte Carlo with projector-augmented wave method for solids
• New insights into the 1D carbon chain through the RPA
• Approaching the basis-set limit of the dRPA correlation energy with explicitly correlated and Projector Augmented-wave methods
• Sampling the reciprocal Coulomb potential in finite and anisotropic cells
• Ground-States for Metals from Converged Coupled Cluster Calculations
• Approaching the Basis Set Limit in Gaussian-Orbital-Based Periodic Calculations with Transferability: Performance of Pure Density Functionals for Simple Semiconductors