Abstract
In this work, we explore the possibility of using computationally inexpensive electronic structure methods, such as semiempirical and DFTB calculations, for the search of the global minimum (GM) structure of chemical systems. The basic prerequisite that these inexpensive methods will need to fulfill is that their lowest energy structures can be used as starting point for a subsequent local optimization at a benchmark level that will yield its GM. If this is possible, one could bypass the global optimization at the expensive method, which is currently impossible except for very small molecules. Specifically, we test our methods with clusters of second row elements including systems of several bonding types, such as alkali, metal, and covalent clusters. The results reveal that the DFTB3 method yields reasonable results and is a potential candidate for this type of applications. Even though the DFTB2 approach using standard parameters is proven to yield poor results, we show that a re-parametrization of only its repulsive part is enough to achieve excellent results, even when applied to larger systems outside the training set.
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Acknowledgments
We are grateful to Compute Canada/WestGrid for computational resources. The support of Centro Federal de Educação Tecnológica de Minas Gerais (CEFET-MG) and Rede Mineira de Química (RQ-MG) are also acknowledged. We acknowledge Prof. Hélio A. Duarte for providing the Acqua computational resources to use the Amsterdam Density Functional (ADF) software to obtain the repulsive potentials and the ACQUA-INCT (http://www.acqua-inct.org).
Funding
This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001, Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) - grants 403352/2016-9 and 305469/2018-5, Fundação de Amparo à Pesquisa do estado de Minas Gerais (FAPEMIG) - grant CEX - APQ-00071-15, and Fundação de Amparo à Pesquisa do Espírito Santo (FAPES) - project CNPq/FAPES PPP 22/2018. DRS thanks NSERC-Canada for ongoing Discovery Grants. LPV thanks the funding from Coimbra Chemistry Center through the CQC-SER-C2-BPD research grant.
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Galvão, B.R.L., Viegas, L.P., Salahub, D.R. et al. Reliability of semiempirical and DFTB methods for the global optimization of the structures of nanoclusters. J Mol Model 26, 303 (2020). https://doi.org/10.1007/s00894-020-04484-4
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DOI: https://doi.org/10.1007/s00894-020-04484-4