Density functional investigation of intermolecular effects on 13C NMR chemical-shielding tensors modeled with molecular clusters

Sean T Holmes; Robbie J Iuliucci; Karl T Mueller; Cecil Dybowski

doi:10.1063/1.4900158

Density functional investigation of intermolecular effects on 13C NMR chemical-shielding tensors modeled with molecular clusters

J Chem Phys. 2014 Oct 28;141(16):164121. doi: 10.1063/1.4900158.

Authors

Sean T Holmes¹, Robbie J Iuliucci², Karl T Mueller³, Cecil Dybowski¹

Affiliations

¹ Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
² Department of Chemistry, Washington and Jefferson College, Washington, Pennsylvania 15301, USA.
³ Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, USA.

PMID: 25362286
DOI: 10.1063/1.4900158

Abstract

A quantum-chemical method for modeling solid-state nuclear magnetic resonance chemical-shift tensors by calculations on large symmetry-adapted clusters of molecules is demonstrated. Four hundred sixty five principal components of the (13)C chemical-shielding tensors of 24 organic materials are analyzed. The comparison of calculations on isolated molecules with molecules in clusters demonstrates that intermolecular effects can be successfully modeled using a cluster that represents a local portion of the lattice structure, without the need to use periodic-boundary conditions (PBCs). The accuracy of calculations which model the solid state using a cluster rivals the accuracy of calculations which model the solid state using PBCs, provided the cluster preserves the symmetry properties of the crystalline space group. The size and symmetry conditions that the model cluster must satisfy to obtain significant agreement with experimental chemical-shift values are discussed. The symmetry constraints described in the paper provide a systematic approach for incorporating intermolecular effects into chemical-shielding calculations performed at a level of theory that is more advanced than the generalized gradient approximation. Specifically, NMR parameters are calculated using the hybrid exchange-correlation functional B3PW91, which is not available in periodic codes. Calculations on structures of four molecules refined with density plane waves yield chemical-shielding values that are essentially in agreement with calculations on clusters where only the hydrogen sites are optimized and are used to provide insight into the inherent sensitivity of chemical shielding to lattice structure, including the role of rovibrational effects.