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American Institute of Physics, The Journal of Chemical Physics, 1(155), p. 011102, 2021

DOI: 10.1063/5.0055575

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Binding curve of the beryllium dimer using similarity-transformed FCIQMC: Spectroscopic accuracy with triple-zeta basis sets

Journal article published in 2021 by Kai Guther ORCID, Aron J. Cohen ORCID, Hongjun Luo ORCID, Ali Alavi ORCID
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

We demonstrate how similarity-transformed full configuration interaction quantum Monte Carlo (FCIQMC) based on the transcorrelated Hamiltonian can be applied to make highly accurate predictions for the binding curve of the beryllium dimer, marking the first case study of a molecular system with this method. In this context, the non-Hermitian transcorrelated Hamiltonian, resulting from a similarity transformation with a Jastrow factor, serves the purpose to effectively address dynamic correlation beyond the used basis set and thus allows for obtaining energies close to the complete basis set limit from FCIQMC already with moderate basis sets and computational effort. Building on results from other explicitly correlated methods, we discuss the role of the Jastrow factor and its functional form, as well as potential sources for size consistency errors, and arrive at Jastrow forms that allow for high accuracy calculations of the vibrational spectrum of the beryllium dimer.