Article Dans Une Revue The Journal of Chemical Physics Année : 2021

A new form of transcorrelated Hamiltonian inspired by range-separated DFT

Emmanuel Giner

Résumé

The present work introduces a new form of explicitly correlated factor in the context of the transcorrelated methods. The new correlation factor is obtained from the r 12 ≈ 0 mathematical analysis of the transcorrelated Hamiltonian, and its analytical form is obtained such that the leading order in 1/r 12 of the scalar part of the effective two-electron potential reproduces the long-range interaction of the range-separated density functional theory. The resulting correlation factor exactly imposes the cusp and is tuned by a unique parameter µ which controls both the depth of the coulomb hole and its typical range in r 12. The transcorrelated Hamiltonian obtained with such a new correlation factor has a straightforward analytical expression depending on the same parameter µ, and its physical contents continuously change by varying µ : one can change from a non divergent repulsive Hamiltonian at large µ to a purely attractive one at small µ. We investigate the convergence of the ground state eigenvalues and right-eigenvectors of such new transcorrelated Hamiltonian as a function of the basis set and as a function of µ on a series of two-electron systems. We found that the convergence towards the complete basis set is much faster for a quite wide range values of µ. We also propose a specific value of µ which essentially reproduce the results obtained with the frozen Gaussian geminal introduced by Ten-No [CPL-330,169 (2000)].

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Dates et versions

hal-03118407 , version 2 (22-01-2021)
hal-03118407 , version 1 (28-11-2021)

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Emmanuel Giner. A new form of transcorrelated Hamiltonian inspired by range-separated DFT. The Journal of Chemical Physics, 2021, 154 (8), ⟨10.1063/5.0044683⟩. ⟨hal-03118407v2⟩
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