We report calculations of the optical rotations of six 6,8-dioxabicyclo[3.2.1]octanes using ab initio density functional theory (DFT). GIAO basis sets are used to ensure origin independence of predicted rotations. Large basis sets including diuse functions are used to minimize basis set error. The signs of [a]D are correctly predicted. Magnitudes dier from experiment by 10±20 degrees [dm (g/cc)] 1 on average. Agree- ment with experiment is improved by inclusion of solvent eects via the Polarized Continuum Model (PCM). The results support the conclusion that DFT/GIAO/PCM calculations of speci®c rotations can be useful in elucidating the absolute con®gurations of chiral molecules.
Prediction of optical rotation using density functional theory: 6,8-diabicyclo [3.2.1] octanes
MENNUCCI, BENEDETTA;TOMASI, IACOPO
2000-01-01
Abstract
We report calculations of the optical rotations of six 6,8-dioxabicyclo[3.2.1]octanes using ab initio density functional theory (DFT). GIAO basis sets are used to ensure origin independence of predicted rotations. Large basis sets including diuse functions are used to minimize basis set error. The signs of [a]D are correctly predicted. Magnitudes dier from experiment by 10±20 degrees [dm (g/cc)] 1 on average. Agree- ment with experiment is improved by inclusion of solvent eects via the Polarized Continuum Model (PCM). The results support the conclusion that DFT/GIAO/PCM calculations of speci®c rotations can be useful in elucidating the absolute con®gurations of chiral molecules.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
