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arXiv · 1101.1790

A quantum Monte Carlo study of the ground state chromium dimer

Kenta Hongo·Ryo Maezono
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Abstract

We report variational and diffusion quantum Monte Carlo (VMC and DMC) studies of the binding curve of the ground-state chromium dimer. We employed various single determinant (SD) or multi-determinant (MD) wavefunctions multiplied by a Jastrow fuctor as a trial/guiding wavefunction. The molecular orbitals (MOs) in the SD were calculated using restricted or unrestricted Hartree-Fock or density functional theory (DFT) calculations where five commonly-used local (SVWN5), semi-local (PW91PW91 and BLYP), and hybrid (B1LYP and B3LYP) functionals were examined. The MD expansions were obtained from the complete-active space SCF, generalized valence bond, and unrestricted configuration interaction methods. We also adopted the UB3LYP-MOs to construct the MD expansion (UB3LYP-MD) and optimized their coefficients at the VMC level. In addition to the wavefunction dependence, we investigated the time-step bias in the DMC calculation and the effects of pseudopotentials and backflow transformation for the UB3LYP-SD case. Some of the VMC binding curves show a flat or quite shallow well bottom, which gets recovered deeper by DMC. All the DMC binding curves have a minimum indicating a bound state, but the comparison of atomic and molecular energies gives rise to a negative binding energy for all the DMC as well as VMC calculations.

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Kenta Hongo, Ryo Maezono. 2011-03-24. A quantum Monte Carlo study of the ground state chromium dimer. https://doi.org/10.1002/qua.23113

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