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

HANNA KJÆR; MONIA R. NIELSEN; GABRIEL I. PAGOLA; MARTA B. FERRARO; PAOLO LAZZERETTI; STEPHAN P. A. SAUER

JOURNAL OF COMPUTATIONAL CHEMISTRY

JOHN WILEY & SONS INC

Lugar: New York; Año: 2012 vol. 33 p. 1781 - 1790

0192-8651

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. VC 2012 Wiley Periodicals, Inc. DOI: 10.1002/jcc.23013