On the performance of Second Order Polarization Propagator methods in the calculation of ¹J_FC and ⁿJ_FH NMR spin-spin coupling constants

This study evaluates the performance of doubles-corrected RPA and HRPA approaches in predicting Nuclear Magnetic Resonance (NMR) coupling constants involving fluorine. Their performance is benchmarked against experimental data and compared with higher-level theoretical methods, specifically SOPPA and SOPPA(CCSD). Additionally, we discuss their performance relative to DFT. We find that RPA(D) is severely constrained by (near) triplet instabilities, while HRPA(D) demonstrates markedly improved stability. Statistical analysis reveals stronger patterns for carbon-fluorine couplings across the methods and systems investigated compared to fluorine-hydrogen couplings. While SOPPA-based methodologies prove to be superior in accuracy, HRPA(D) shows promising performance in reducing the computational burden of these calculations, albeit with a tendency to underestimate the coupling strength. These findings highlight the potential of HRPA(D) as a practical alternative to SOPPA methods even for such difficult properties as NMR spin-spin coupling constants involving fluorine, emphasizing its role in improving predictive accuracy and efficiency across diverse chemical environments.