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Reference spaces for multireference coupled-cluster theory: the challenge of the CoH molecule

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Abstract

In multireference calculations on transition metal compounds, large active spaces including a second set of d orbitals are often used. However, with the increase in the system size and the complexity of the method, such calculations quickly become impractical. In this work, we looked for an inner valence active space for atomic cobalt and its hydride that correctly describes the transition energies among states with distinct configurations. Potential energy curves for the CoH molecule were obtained using a fixed reference space, where the orbitals are optimised only for the isolated atoms, avoiding undesirable sudden variations of the active orbitals. The calculations made use of the multireference configuration interaction (MRCI) and coupled-cluster (MRCC) theories. The accuracy of these calculations is carefully analysed, and we show that MRCC results are accurate, although not all electronic states are quantitatively described at the MRCI level. We conclude that the use of the fixed reference space is a viable approach to reduce the computational cost when large active spaces are prohibitive. Finally, a careful comparison of the present results with experimental values is carried out.

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Acknowledgements

We are very thankful to Andreas Köhn for the release of the GeCCo programme and to Pradipta Kumar Samanta for the assistance on the calculations of icMRCC dipole moments. Y.A.A. is grateful to Márcio Fabiano da Silva for the kind support. This research has been supported by Grants #2017/21199-0, #2018/04617-6 and #2018/14629-1, São Paulo Research Foundation (FAPESP). This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil (CAPES)—Finance Code 001.

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  1. Center for Mathematics Computing and Cognition, Federal University of ABC (UFABC), Avenida dos Estados 5001, Santo André, Brazil

    Matheus Morato F. de Moraes & Yuri Alexandre Aoto

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  1. Matheus Morato F. de Moraes
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Correspondence to Yuri Alexandre Aoto.

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This work is dedicated to Professor Fernando Rei Ornellas on the occasion of his 70th birthday.

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de Moraes, M.M.F., Aoto, Y.A. Reference spaces for multireference coupled-cluster theory: the challenge of the CoH molecule. Theor Chem Acc 139, 71 (2020). https://doi.org/10.1007/s00214-020-2584-1

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