6533b826fe1ef96bd128469d
RESEARCH PRODUCT
A computationally feasible quantum chemical model for 13C NMR chemical shifts of PCB-derived carboxylic acids.
Vadim P. BoyarskiyKari TuppurainenVladimir NikiforovSvetlana A. LaninaErkki KolehmainenTatiana E. ZheskoElina SievänenKatri Laihiasubject
Models MolecularEnvironmental EngineeringMagnetic Resonance SpectroscopyHealth Toxicology and MutagenesisCarboxylic AcidsQuantum chemistryAtomic orbitalEnvironmental ChemistryQuantitative Biology::BiomoleculesCarbon IsotopesMolecular StructureHydrogen bondChemistryChemical shiftPublic Health Environmental and Occupational HealthGeneral MedicineGeneral ChemistryHydrogen atomCarbon-13 NMRPollutionPolychlorinated BiphenylsModels ChemicalSolventsPhysical chemistryQuantum TheoryDensity functional theoryEnvironmental PollutantsSolvent effectsSoftwaredescription
Two quantum chemical models have been derived for the prediction of 13C NMR chemical shifts of novel PCB acids obtained from PCBs by catalytic carbonylation. 13C isotropic shielding constants were calculated employing the GIAO (gauge-independent atomic orbital) method with density functional theory (DFT). The best results were obtained by cluster calculations, which took the solvent effects into account properly. In this approach, a solvent molecule (acetone) was attached by a hydrogen bond to every hydrogen atom present in a PCB acid, and the geometry of the molecular cluster was optimized employing the AM1 method. For 158 chemical shifts, the cross-validated standard error was 2.8 ppm and the cross-validated correlation coefficient was 0.94.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2004-12-27 | Chemosphere |