Quantum Monte Carlo study of the energetics of small hydrogenated and fluoride lithium clusters

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2016

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An investigation of the energetics of small lithium clusters doped either with a hydrogen or with a fluorine atom as a function of the number of lithium atoms using fixed-node diffusion quantum Monte Carlo (DMC) simulation is reported. It is found that the binding energy (BE) for the doped clusters increases in absolute values leading to a more stable system than for the pure ones in excellent agreement with available experimental measurements. The BE increases for pure, remains almost constant for hydrogenated, and decreases rapidly toward the bulk lithium for the fluoride as a function of the number of lithium atoms in the clusters. The BE, dissociation energy as well as the second difference in energy display a pronounced odd–even oscillation with the number of lithium atoms. The electron correlation inverts the odd–even oscillation pattern for the doped in comparison with the pure clusters and has an impact of 29%–83% to the BE being higher in the pure cluster followed by the hydrogenated and then by the fluoride. The dissociation energy and the second difference in energy indicate that the doped cluster Li3H is the most stable whereas among the pure ones the more stable are Li2, Li4, and Li6. The electron correlation energy is crucial for the stabilization of Li3H. © 2016 Wiley Periodicals, Inc.

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MOREIRA, N. L. et al. Quantum Monte Carlo study of the energetics of small hydrogenated and fluoride lithium clusters. Journal of Computational Chemistry, New York, v. 37, n. 17, p.1531-1536, 2016. DOI: 10.1002/jcc.24363. Disponível em: https://onlinelibrary.wiley.com/doi/10.1002/jcc.24363. Acesso em: 19 jan. 2024.