Indirect nuclear spin-spin couplings with third-order contributions added to the SOPPA method.

Abstract

In this article, a modification of the second-order polarization propagator approximation (SOPPA) method is introduced and illustrated for the calculation of the indirect nuclear spin-spin couplings. The standard SOPPA method, although cheaper in terms of computational cost, offers less accurate results than the ones obtained with coupled cluster methods. A new method, named SOPPA+A3-3, was therefore developed by adding the terms of the third-order A matrix that rely on the second-order double amplitudes. The performance of this third-order contribution was studied using the coupled cluster singles and doubles method as a reference, calculating the spin-spin couplings of molecules of diverse sizes and compositions, and comparing them to the SOPPA method. The results show that inclusion of this third-order contribution gives more accurate results than the standard SOPPA method with a level of accuracy close to that of the coupled cluster method with only a small increase in the computational cost of the response calculation that dominates the computational cost for small- to medium-sized molecules. The implementation of the first contributions to the third-order polarization propagator approximation in the Dalton program, thus, already shows a significant change in these molecular properties over those obtained with the standard SOPPA method.