TY - JOUR
T1 - On the performance of HRPA(D) for NMR spin-spin coupling constants
T2 - Smaller molecules, aromatic and fluoroaromatic compounds
AU - Jessen, Louise Møller
AU - Sauer, Stephan P. A.
PY - 2024/2/8
Y1 - 2024/2/8
N2 - In this study, the performance of the doubles-corrected higher random-phase approximation (HRPA(D)) has been investigated in calculations of NMR spin-spin coupling constants (SSCCs) for 58 molecules with the experimental values used as the reference values. HRPA(D) is an approximation to the second-order polarization propagator approximation (SOPPA), and is therefore computationally less expensive than SOPPA. HRPA(D) performs comparable and sometimes even better than SOPPA, and therefore when calculating SSCCs it should be considered as an alternative to SOPPA. Furthermore, it was investigated whether a CCSD(T) or MP2 geometry optimization was optimal for a SOPPA and a HRPA(D) SSCCs calculation for 8 smaller molecules. CCSD(T) is the optimal geometry optimization for the SOPPA calculation, and MP2 was optimal for the HRPA(D) SSCC calculations.
AB - In this study, the performance of the doubles-corrected higher random-phase approximation (HRPA(D)) has been investigated in calculations of NMR spin-spin coupling constants (SSCCs) for 58 molecules with the experimental values used as the reference values. HRPA(D) is an approximation to the second-order polarization propagator approximation (SOPPA), and is therefore computationally less expensive than SOPPA. HRPA(D) performs comparable and sometimes even better than SOPPA, and therefore when calculating SSCCs it should be considered as an alternative to SOPPA. Furthermore, it was investigated whether a CCSD(T) or MP2 geometry optimization was optimal for a SOPPA and a HRPA(D) SSCCs calculation for 8 smaller molecules. CCSD(T) is the optimal geometry optimization for the SOPPA calculation, and MP2 was optimal for the HRPA(D) SSCC calculations.
KW - Faculty of Science
KW - NMR
KW - spin-spin coupling constants
KW - HRPA(D)
U2 - 10.48550/arXiv.2312.00705
DO - 10.48550/arXiv.2312.00705
M3 - Journal article
C2 - 38341775
VL - 160
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
SN - 0021-9606
IS - 6
M1 - 064102
ER -