Nuclear magnetic resonance J coupling constant polarizabilities of hydrogen peroxide: A basis set and correlation study

Abstract

In this article, 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 nuclear magnetic resonance (NMR) indirect nuclear spin-spin coupling constant with respect to an external electric field and play an important role for both chiral discrimination and solvation effects on NMR coupling constants. In this study, we illustrate the effects 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 perform calculations with the largest available basis sets optimized for the calculation of NMR coupling constants. We find a systematic but rather slow convergence with the one-electron basis set and that augmentation functions are required. We observe also large and nonsystematic correlation effects with significant differences between the density functional and wave function theory methods.

RPA(D) and HRPA(D): Two new models for calculations of NMR indirect nuclear spin–spin coupling constants

“…Nowadays, measurements of NMR spectra are often accompanied by calculations of chemical shifts and indirect nuclear spin–spin coupling constants, the two parameters determining a solution or gas phase NMR spectrum . In particular, the coupling constants can provide important information on, for example, the stereochemistry of compounds, tautomer equilibria, nonbonded interactions, or potentially even chiral discrimination …”

On the discrepancy between theory and experiment for the F–F spin–spin coupling constant of difluoroethyne

“…We call the latter aug-ccJ-pVXZ in agreement with earlier practice. 51,54 Single point calculations have been made using a number of different basis sets for all methods. Only by carefully investigating how the calculated value depends on the size of the basis set, can we know how our results are changed by this essentially non-physical parameter.…”

The aug‐cc‐pVTZ‐J basis set for the p‐block fourth‐row elements Ga, Ge, As, Se, and Br

“…Nuclear magnetic resonance (NMR) spectroscopy is the most employed tool when characterizing and probing the structure of both organic and inorganic compounds in solution. Lately, solution or gas-phase NMR experiments are often accompanied by ab initio calculations of the indirect nuclear spin-spin coupling constants or the chemical shifts in order to confirm the identity of the studied compounds [1] or to obtain further information on tautomer equilibria, [2] nonbonded interactions, [3,4] and stereochemistry, [5][6][7][8][9] to name a few.…”