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A case study of density functional theory and domain-based local pair natural orbital coupled cluster for vibrational effects on EPR hyperfine coupling constants: vibrational perturbation theory versus ab initio molecular dynamics

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Auer,  Alexander A.
Research Group Auer, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Tran,  Van Anh
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Stoychev,  Georgi L.
Research Group Auer, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Auer, A. A., Tran, V. A., Sharma, B., Stoychev, G. L., Marx, D., & Neese, F. (2020). A case study of density functional theory and domain-based local pair natural orbital coupled cluster for vibrational effects on EPR hyperfine coupling constants: vibrational perturbation theory versus ab initio molecular dynamics. Molecular Physics, 118(19-20): e1797916. doi:10.1080/00268976.2020.1797916.


Cite as: http://hdl.handle.net/21.11116/0000-0007-64FC-D
Abstract
Local approximations of high-level ab initio methods make superior accuracy in the computation of molecular properties accessible by drastically decreasing computational times. As a consequence, these methods become applicable not only for large systems but also in schemes for which large numbers of calculations are necessary. In this work, we apply a recently developed open-shell implementation of the domain-based pair natural orbital coupled cluster singles doubles (DLPNO-CCSD) approach for the computation of vibrational corrections to the isotropic values of electron paramagnetic resonance (EPR) hyperfine coupling constants. We assess density functional theory (DFT) and DLPNO-CCSD approaches using two common but very different schemes: (1) vibrational perturbation theory based on equilibrium geometries, and (2) explicit canonical ensemble averages using configuration snapshots sampled from revPBE0-D3(0) ab initio molecular dynamics simulations. Both approaches are found to yield very similar results for the spin probe 2,2,3,4,5,5-hexamethylperhydroimidazol-1-oxyl (HMI) and are both feasible for systems of around 30 atoms. However, the numerical stability required for higher derivatives can become a limitation for local correlation methods in the case of vibrational perturbation theory.