Biorthonormal orbital optimization with a cheap core-electron free three-body correlation factor for Quantum Monte Carlo and Transcorrelation - Faculté des Sciences de Sorbonne Université
Journal Articles Journal of Chemical Theory and Computation Year : 2023

Biorthonormal orbital optimization with a cheap core-electron free three-body correlation factor for Quantum Monte Carlo and Transcorrelation

Abstract

We introduce a novel three-body correlation factor that is designed to vanish in the core region around each nucleus and approach a universal two-body correlation factor for valence electrons. The Transcorrelated Hamiltonian is used to optimize the orbitals of a single Slater determinant within a biorthonormal framework. The Slater-Jastrow wave function is optimized on a set of atomic and molecular systems containing both second-row elements and $3d$ transition metal elements. The optimization of the correlation factor and the orbitals, along with increasing the basis set, results in a systematic lowering of the Variational Monte Carlo energy for all systems tested. Importantly, the optimal parameters of the correlation factor obtained for atomic systems are transferable to molecules. Additionally, the present correlation factor is computationally efficient, using a mixed analytical-numerical integration scheme that reduces the costly numerical integration from $\mathbb{R}^6$ to $\mathbb{R}^3$.
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Dates and versions

hal-04020133 , version 1 (17-09-2024)

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Abdallah Ammar, Anthony Scemama, Emmanuel Giner. Biorthonormal orbital optimization with a cheap core-electron free three-body correlation factor for Quantum Monte Carlo and Transcorrelation. Journal of Chemical Theory and Computation, 2023, 19 (15), pp.4883-4896. ⟨10.1021/acs.jctc.3c00257⟩. ⟨hal-04020133⟩
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