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Title: Density functional investigation of intermolecular effects on {sup 13}C NMR chemical-shielding tensors modeled with molecular clusters

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 {sup 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 valuesmore » 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.« less
Authors:
;  [1] ;  [2] ;  [3] ;  [4]
  1. Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716 (United States)
  2. Department of Chemistry, Washington and Jefferson College, Washington, Pennsylvania 15301 (United States)
  3. Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802 (United States)
  4. (United States)
Publication Date:
OSTI Identifier:
22310738
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; CARBON 13; DENSITY FUNCTIONAL METHOD; MOLECULAR CLUSTERS; MOLECULES; NUCLEAR MAGNETIC RESONANCE; ORGANIC MATTER; SENSITIVITY; SIMULATION; SOLIDS; SPACE GROUPS; TENSORS