On the convergence of zero-point vibrational corrections to nuclear shieldings and shielding anisotropies towards the complete basis set limit in water
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On the convergence of zero-point vibrational corrections to nuclear shieldings and shielding anisotropies towards the complete basis set limit in water. / Faber, Rasmus; Buczek, Aneta; Kupka, Teobald; Sauer, Stephan P. A.
I: Molecular Physics, Bind 115, Nr. 1-2, 2017, s. 144-160.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - On the convergence of zero-point vibrational corrections to nuclear shieldings and shielding anisotropies towards the complete basis set limit in water
AU - Faber, Rasmus
AU - Buczek, Aneta
AU - Kupka, Teobald
AU - Sauer, Stephan P. A.
PY - 2017
Y1 - 2017
N2 - The method and basis set dependence of zero-point vibrational corrections (ZPVC) to NMR shielding constants and anisotropies has been investigated using water as a test system. A systematic comparison has been made using the Hartree-Fock (HF), second-order Møller-Plesset perturbation theory (MP2), coupled cluster singles and doubles (CCSD), coupled cluster singles and doubles with perturbative triples corrections (CCSD(T)) and Kohn-Sham density functional theory (DFT) with the B3LYP exchange-correlation functional methods in combination with the second order vibrational perturbation theory (VPT2) approach for the vibrational corrections. As basis sets the correlation consistent basis sets cc-pVXZ, aug-ccpVXZ, cc-pCVXZ and aug-cc-pCVXZ with X = D, T, Q, 5, 6 and the polarization consistent basis sets aug-pc-n and aug-pcS-n with n = 1, 2, 3, 4 were employed. Our results show, that basis set convergence of the vibrational corrections is not monotonic and that very large basis sets are needed before a reasonable extrapolation to the basis set limit can be performed. Furthermore, our results suggest that coupled cluster methods and a decent basis set are required before the error of the electronic structure approach is lower than the inherent error of the VPT2 approximation.
AB - The method and basis set dependence of zero-point vibrational corrections (ZPVC) to NMR shielding constants and anisotropies has been investigated using water as a test system. A systematic comparison has been made using the Hartree-Fock (HF), second-order Møller-Plesset perturbation theory (MP2), coupled cluster singles and doubles (CCSD), coupled cluster singles and doubles with perturbative triples corrections (CCSD(T)) and Kohn-Sham density functional theory (DFT) with the B3LYP exchange-correlation functional methods in combination with the second order vibrational perturbation theory (VPT2) approach for the vibrational corrections. As basis sets the correlation consistent basis sets cc-pVXZ, aug-ccpVXZ, cc-pCVXZ and aug-cc-pCVXZ with X = D, T, Q, 5, 6 and the polarization consistent basis sets aug-pc-n and aug-pcS-n with n = 1, 2, 3, 4 were employed. Our results show, that basis set convergence of the vibrational corrections is not monotonic and that very large basis sets are needed before a reasonable extrapolation to the basis set limit can be performed. Furthermore, our results suggest that coupled cluster methods and a decent basis set are required before the error of the electronic structure approach is lower than the inherent error of the VPT2 approximation.
KW - Faculty of Science
KW - Water
KW - NMR spectrocopy
KW - NMR; chemical shift
KW - Density functional theory
KW - DFT calculations
KW - vibrational correction
KW - Coupled Cluster
KW - Basis sets
U2 - 10.1080/00268976.2016.1210831
DO - 10.1080/00268976.2016.1210831
M3 - Journal article
VL - 115
SP - 144
EP - 160
JO - Molecular Physics
JF - Molecular Physics
SN - 0026-8976
IS - 1-2
ER -
ID: 163092547