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Self-Consistent Field Calculation of Nuclear Magnetic Resonance Chemical Shielding Constants Using Gauge-Including Atomic Orbitals and Approximate Two-Electron Integrals

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Stoychev,  Georgi L.
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Auer,  Alexander A.
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Izsák,  Róbert
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Stoychev, G. L., Auer, A. A., Izsák, R., & Neese, F. (2018). Self-Consistent Field Calculation of Nuclear Magnetic Resonance Chemical Shielding Constants Using Gauge-Including Atomic Orbitals and Approximate Two-Electron Integrals. Journal of Chemical Theory and Computation, 14(2), 619-637. doi:10.1021/acs.jctc.7b01006.


Cite as: http://hdl.handle.net/21.11116/0000-0007-6E47-F
Abstract
The chain-of-spheres method (COS) for approximating two-electron integrals is applied to Hartree–Fock and density functional theory calculations of nuclear magnetic resonance chemical shielding tensors, based on gauge-including atomic orbitals. The accuracy of the approximation is compared to that of the resolution of the identity (RI) approach, using a benchmark test set of 15 small molecules. Reasonable auxiliary basis sets and grid sizes are selected on the basis of a careful investigation of how approximating each of the two-electron terms in the self-consistent field (SCF) and coupled perturbed SCF equations affects the calculated shielding constants. It is found that the errors are linearly additive but can have either sign. The mean absolute relative error due to applying the RI/COS approximations with the chosen settings to all two-electron terms is on the order of 0.01% and therefore negligible compared to the errors due to basis set incompleteness (∼1%) and the method used (10–50%). Several larger organic systems are used to assess the efficiency of the RI approximation for both Coulomb- and exchange-type integrals (RIJK) as well as a combination of RI for Coulomb and COS for exchange contributions (RIJCOSX). The RIJK approximation is more efficient for small molecules, while for systems of over 100 electrons and 1000 basis functions, the RIJCOSX approximation is superior.