Pople style basis sets for the calculation of NMR spin-spin coupling constants: the 6-31G-J and 6-311G-J basis sets

TY - JOUR

T1 - Pople style basis sets for the calculation of NMR spin-spin coupling constants: the 6-31G-J and 6-311G-J basis sets

AU - Kjær, Hanna

AU - Sauer, Stephan P. A.

PY - 2011/12/13

Y1 - 2011/12/13

N2 - We present a modification of the small and popular Pople basis sets, 6-31G and 6-311G, for density functional theory calculations of Fermi contact dominated NMR indirect nuclear spin-spin coupling constants. These new basis sets, 6-31G-J and 6-311G-J, contain twice the number of contracted s-type functions but the same number of contracted p-type functions as the original Pople basis set. For our test set of 12 one-, two- and three-bond coupling constants, the new basis sets augmented with the standard diffuse and polarization functions, i.e., the 6-31+G*-J and 6-311++G**-J basis sets, lead to a maximum deviation of 5 and 2 Hz, respectively, compared to results obtained with the 6 or more times larger aug-pcJ-4 basis set. In correlated wave function calculations using the second-order polarization propagator approximation, the deviations with respect to the aug-ccJ-pVQZ basis set are 8 and 3 Hz and thus slightly larger.

AB - We present a modification of the small and popular Pople basis sets, 6-31G and 6-311G, for density functional theory calculations of Fermi contact dominated NMR indirect nuclear spin-spin coupling constants. These new basis sets, 6-31G-J and 6-311G-J, contain twice the number of contracted s-type functions but the same number of contracted p-type functions as the original Pople basis set. For our test set of 12 one-, two- and three-bond coupling constants, the new basis sets augmented with the standard diffuse and polarization functions, i.e., the 6-31+G*-J and 6-311++G**-J basis sets, lead to a maximum deviation of 5 and 2 Hz, respectively, compared to results obtained with the 6 or more times larger aug-pcJ-4 basis set. In correlated wave function calculations using the second-order polarization propagator approximation, the deviations with respect to the aug-ccJ-pVQZ basis set are 8 and 3 Hz and thus slightly larger.

U2 - 10.1021/ct200546q

DO - 10.1021/ct200546q

M3 - Journal article

C2 - 26598352

SN - 1549-9618

VL - 7

SP - 4070

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

IS - 12

ER -