Quantum Monte Carlo Calculation of the Binding Energy of the Beryllium Dimer

Publication Information:

Deible, M.J., M. Kessler, K. E. Gasperich, K. D. Jordan, “Quantum Monte Carlo calculation of the binding energy of the beryllium dimer,” J. Chem. Phys., 2015, 143 (8), 084116.

Year: 2016

The accurate calculation of the binding energy of the beryllium dimer is a challenging theoretical problem. In this study, the binding energy of Be2 is calculated using the diffusion Monte Carlo (DMC) method, using single Slater determinant and multiconfigurational trial functions. DMC calculations using single-determinant trial wave functions of orbitals obtained from density functional theory calculations overestimate the binding energy, while DMC calculations using Hartree-Fock or CAS(4,8), complete active space trial functions significantly underestimate the binding energy. In order to obtain an accurate value of the binding energy of Be2 from DMC calculations, it is necessary to employ trial functions that include excitations outside the valence space. Our best estimate DMC result for the binding energy of Be2, obtained by using configuration interaction trial functions and extrapolating in the threshold for the configurations retained in the trial function, is 908 cm−1, only slightly below the 935 cm−1 value derived from experiment.

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