Indirect nuclear spin-spin couplings with third order contributions added to the SOPPA method
Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
Standard
Indirect nuclear spin-spin couplings with third order contributions added to the SOPPA method. / Sanz Rodrigo, Javier; Hillers-Bendtsen, Andreas Erbs; Kjeldal, Frederik Ørsted; Høyer, Nicolai Machholdt ; Mikkelsen, Kurt Valentin; Sauer, Stephan P. A.
I: The Journal of Chemical Physics, Bind 158, Nr. 12, 124118, 28.03.2023.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
Harvard
APA
Vancouver
Author
Bibtex
}
RIS
TY - JOUR
T1 - Indirect nuclear spin-spin couplings with third order contributions added to the SOPPA method
AU - Sanz Rodrigo, Javier
AU - Hillers-Bendtsen, Andreas Erbs
AU - Kjeldal, Frederik Ørsted
AU - Høyer, Nicolai Machholdt
AU - Mikkelsen, Kurt Valentin
AU - Sauer, Stephan P. A.
PY - 2023/3/28
Y1 - 2023/3/28
N2 - 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 CCSD 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 small increase of 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 (TOPPA) in the Dalton program thus already shows a significant change in these molecular properties over those obtained with the standard SOPPA method.
AB - 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 CCSD 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 small increase of 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 (TOPPA) in the Dalton program thus already shows a significant change in these molecular properties over those obtained with the standard SOPPA method.
U2 - 10.1063/5.0140117
DO - 10.1063/5.0140117
M3 - Journal article
C2 - 37003784
VL - 158
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
SN - 0021-9606
IS - 12
M1 - 124118
ER -
ID: 338446276