TY - JOUR

T1 - Nuclear magnetic resonance J coupling constant polarizabilities of hydrogen peroxide

T2 - a basis set and correlation study

AU - Kjær, Hanna

AU - Nielsen, Monia R.

AU - Pagola, Gabriel I.

AU - Ferraro, Marta B.

AU - Lazzeretti, Paolo

AU - Sauer, Stephan P. A.

PY - 2012

Y1 - 2012

N2 - In this paper we present the so far most extended investigation of the calculation of the coupling constant polarizability of a molecule. The components of the coupling constant polarizability are derivatives of the NMR indirect nuclear spin-spin coupling constant with respect to an external electric ¿eld and play an important role for both chiral discrimination and solvation e¿ects on NMR coupling constants. In this study we illustrate the e¿ects of one-electron basis sets and electron correlation both at the level of density functional theory as well as second order polarization propagator approximation for the small molecule hydrogen peroxide, which allowed us to carry out calculations with the largest available basis sets optimized for the calculation of NMR coupling constants. We ¿nd a systematic but rather slow convergence with the one-electron basis set and that augmentation functions are required. We observe also large and non-systematic correlation e¿ects with signi¿cant di¿erences between the density functional and wave function theory methods.

AB - In this paper we present the so far most extended investigation of the calculation of the coupling constant polarizability of a molecule. The components of the coupling constant polarizability are derivatives of the NMR indirect nuclear spin-spin coupling constant with respect to an external electric ¿eld and play an important role for both chiral discrimination and solvation e¿ects on NMR coupling constants. In this study we illustrate the e¿ects of one-electron basis sets and electron correlation both at the level of density functional theory as well as second order polarization propagator approximation for the small molecule hydrogen peroxide, which allowed us to carry out calculations with the largest available basis sets optimized for the calculation of NMR coupling constants. We ¿nd a systematic but rather slow convergence with the one-electron basis set and that augmentation functions are required. We observe also large and non-systematic correlation e¿ects with signi¿cant di¿erences between the density functional and wave function theory methods.

KW - Faculty of Science

KW - NMR

KW - Quantum Chemistry

KW - chirality

KW - Computational Chemistry

U2 - 10.1002/jcc.23013

DO - 10.1002/jcc.23013

M3 - Journal article

C2 - 22618604

VL - 33

SP - 1845

EP - 1853

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

SN - 0192-8651

IS - 23

ER -