RPA(D) and HRPA(D): Two new models for calculations of NMR indirect nuclear spin-spin coupling constants

SCHNACK-PETERSEN, ANNA KRISTINA; HAASE, PI A. B.; FABER, RASMUS; PROVASI, PATRICIO F.; SAUER, STEPHAN P. A.

JOURNAL OF COMPUTATIONAL CHEMISTRY

JOHN WILEY & SONS INC

Lugar: New York; Año: 2018 vol. 39 p. 2647 - 2666

0192-8651

In this article, the RPA(D) and HRPA(D) models for the calculation of linear response functions are presented. The performance of the new RPA(D) and HRPA(D) models is compared to the performance of the established RPA, HRPA, and SOPPA models in calculations of indirect nuclear spin?spin coupling constants using the CCSD model as a reference. The doubles correction offers a significant improvement on both the RPA and HRPA models; however, the improvement is more dramatic in the case of the RPA model. For all coupling types investigated in this study, the results obtained using the HRPA(D) model are comparable in accuracy to those given by the SOPPA model, while requiring between 30% and 90% of the calculation time needed forSOPPA. The RPA(D) model, while of slightly lower accuracy compared to the CCSD model than HRPA(D), offered calculation times of only approximately 25% of those required for SOPPA for all the investigated molecules.