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

Abstract

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 r12 ≈ 0 mathematical analysis of the transcorrelated Hamiltonian, and its analytical form is obtained such that the leading order in 1/r12 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 r12. 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 a 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 toward the complete basis set is much faster for quite a wide range of values of μ. We also propose a specific value of μ, which essentially reproduces the results obtained with the frozen Gaussian geminal introduced by Ten-no [Chem. Phys. Lett. 330, 169 (2000)].