Correlated ab Initio Spin Densities for Larger Molecules: Orbital-Optimized 
Spin-Component-Scaled MP2 Method

Kossmann, Simone; Neese, Frank

doi:10.1021/jp105647c

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Correlated ab Initio Spin Densities for Larger Molecules: Orbital-Optimized Spin-Component-Scaled MP2 Method

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Kossmann, S., & Neese, F. (2010). Correlated ab Initio Spin Densities for Larger Molecules: Orbital-Optimized Spin-Component-Scaled MP2 Method. The Journal of Physical Chemistry A, 114(43), 11768-11781. doi:10.1021/jp105647c.

Cite as: https://hdl.handle.net/21.11116/0000-0008-0F8B-C

Abstract

The performance of the orbital-optimized MP2 method (OO-MP2) and its spin-component-scaled variant is investigated for the prediction of atomic and molecular hyperfine coupling constants (hfccs). The calculated hfccs are compared to experimental as well as to CCSD(T) reference results. The OO-MP2 isotropic hfccs for a series of small radicals are almost of CCSD quality but are obtained with iterative O (N⁵) effort. The dipolar hfccs are less well predicted by the OO-MP2 methods, whereas spin-component scaling improves the description of the hyperfine structure. The spin contamination in the OO-MP2 wave function is drastically reduced compared to the standard unrestricted Hartree−Fock wave function. The applicability of the OO-MP2 to fairly large systems is demonstrated for the solvated p-benzosemiquinone radical anion, where calculations with almost 2000 basis functions have been performed.