Segmented Contracted Basis Sets Optimized for Nuclear Magnetic Shielding

Abstract

A family of segmented contracted basis sets is proposed, denoted pcSseg-n, which are optimized for calculating nuclear magnetic shielding constants. For the elements H-Ar, these are computationally more efficient than the previously proposed general contracted pcS-n basis sets, and the new basis sets are extended to also include the elements K-Kr. The pcSseg-n basis sets are optimized at the density functional level of theory, but it has been shown previously that these property-optimized basis sets are also suitable for calculating shielding constants with correlated wave function methods. The pcSseg-n basis sets are available in qualities ranging from (unpolarized) double-ζ to pentuple-ζ quality and should be suitable for both routine and benchmark calculations of nuclear magnetic shielding constants. The ability to rigorously separate basis set and method errors should aid in developing more accurate methods.

Computational 1H NMR: Part 1. Theoretical background

“…In view of the overwhelming amount of references on particular basis sets, herewith, we will give only some key references for Pople's sets, [51,52] Dunning's sets, [53][54][55][56][57][58][59][60][61][62][63] Jensen's sets, [64][65][66][67][68][69][70] and relativistic Dyall's basis sets. [71][72][73][74][75][76][77][78][79][80] The latter sets are used in relativistic calculations, which are discussed in Section 2.6.…”

Balancing Donor‐Acceptor and Dispersion Effects in Heavy Main Group Element π Interactions: Effect of Substituents on the Pnictogen⋅⋅⋅π Arene Interaction

“…NMR chemical shifts were computed using the M06L, [44] TPSS, [45] B3LYP, [46][47][48] and KT2 [49] density functionals in conjunction with the pcSseg-3 [50] basis set for lighter elements and the Sapporo-DKH3-TZP-2012 [51] basis set for the bismuth atom.…”

On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide: a frustrated solvent

“…?g(d,p) basis set (McLean and Chandler 1980;Krishnan et al 1980). NMR chemical shifts were calculated with the gaugeindependent atomic orbitals (GIAO) method using the same density functional with the pcSseg-2 basis set (Jensen 2015), both of which are optimized for chemical shift calculations. In all calculations, a polarizable continuum solvent model corresponding to DMSO was included using the SCRF method.…”