Basis Set Convergence of Indirect Spin–Spin Coupling Constants in the Kohn–Sham Limit for Several Small Molecules

Abstract

The performance of more than 40 density functionals in predicting indirect spin-spin coupling constants (SSCCs) in the Kohn-Sham basis set limit was tested. For comparison, similar calculations were performed using the RHF, SOPPA, SOPPA(CC2), and SOPPA(CCSD) methods, and the results were estimated toward the complete basis set (CBS) limit. The SSCCs of nine small molecules (N(2), CO, CO(2), NH(3), CH(4), C(2)H(2), C(2)H(4), C(2)H(6), and C(6)H(6)) were calculated using the dedicated Jensen pcJ-n polarization-consistent basis sets and used for the CBS limit estimations within the Kohn-Sham limit. These CBS results were compared with calculations using the aug-cc-pVTZ-J basis set. Among the 41 studied DFT methods, the tHCTHhyb, HSEh1PBE, HSE2PBE, wB97XD, wB97, and wB97X functionals reproduced accurately the experimental (1)J(XH) SSCCs and (3)J(HH60) and (2)J(HH(gem)) in ethane. Similarly, the functionals HSEh1PBE, HSE2PBE, wB97XD, wB97, and wB97X predicted accurately (1)J(CC), and B98, B97-1, B97-2, PBE1PBE, B1LYP, and O3LYP provided accurate (1)J(CO) results in the CO molecule. A very good performance for the calculation of the SSCCs based on the use of the relatively small basis set aug-cc-pVTZ-J was observed.

NMR Spectroscopic Study of Tautomerism in Solution and in the Solid State

“…For δ and J information, special basis sets were developed (reviewed by Jensen) [146] for computing the NMR parameters with ''analytical precision''. CCSD-based computation obviously is the gold standard, but the less expensive aug-cc-pVTZ-J basis set results in J values that compare very well with the CBS estimates [147], considering the solvent, if necessary, as well [148].…”

Theoretical prediction of structural, vibrational and NMR parameters of plastic optical fiber (POF) material precursors. Cis and trans perhydro- and perfluoro-2-methylene-4,5-dimethyl-1,3-dioxolanes

“…The aug-pcJ-2 belongs to the Jensen's family of basis sets [57] which produce SSCC values regularly converging toward CBS limit [29,53,77]. It also yields very accurate nuclear isotropic shieldings [52].…”

“…It is well known that the NMR shieldings (and to the less extend the chemical shifts) and indirect spin-spin coupling constants are very sensitive to the density functional type used and the basis set construction [50][51][52][53][54][55]. Among the basis sets tailored for accurate calculations of nuclear shieldings and spin-spin coupling parameters are systematically improved pcS-n [56] and pcJ-n [57] series of basis sets (n = 0, 1, 2, 3 and 4).…”

Theoretical and experimental NMR studies on muscimol from fly agaric mushroom (Amanita muscaria)

“…Thus, the carbon-proton couplings cannot be used to distinguish between the three studied forms of muscimol in DMSO. Can one improve the accuracy of theoretical prediction of SSCC parameters101 ? The rovibrational corrections could in principle improve the agreement between theory and experiment.…”

“…However, in comparison to nuclear shieldings, it is much more difficult to calculate the correction to the coupling constants101 . Besides, in our opinion, these corrections could consistently improve results obtained with the more advanced theoretical methods(SOPPA 102 or EOM CCSD 103,104 ) but not those, obtained from DFT approach 101 , which is somehow semiempirical.…”