2 research outputs found
Inverted Carbon Geometries: Challenges to Experiment and Theory
Disproving a long
C–C-bond textbook example: The reported
1.643 Å C–C bond in 5-cyano-1,3-dehydroadamantane was
redetermined and “only” amounts to 1.584 Å. While
this value is well reproduced with <i>ab initio</i> methods,
some common DFT approaches perform poorly and are only consistent
with CCSDÂ(T)/cc-pVTZ optimizations for noninverted carbons. Large
deviations from experiment were also found for other molecules with
atypical electron density distributions, e.g., cubane, bicyclo[2.2.0]Âhexane,
and bicyclo[2.1.0]- and bicyclo[1.1.1]Âpentane, thereby presenting
challenging structures for some DFT implementations
Inverted Carbon Geometries: Challenges to Experiment and Theory
Disproving a long
C–C-bond textbook example: The reported
1.643 Å C–C bond in 5-cyano-1,3-dehydroadamantane was
redetermined and “only” amounts to 1.584 Å. While
this value is well reproduced with <i>ab initio</i> methods,
some common DFT approaches perform poorly and are only consistent
with CCSDÂ(T)/cc-pVTZ optimizations for noninverted carbons. Large
deviations from experiment were also found for other molecules with
atypical electron density distributions, e.g., cubane, bicyclo[2.2.0]Âhexane,
and bicyclo[2.1.0]- and bicyclo[1.1.1]Âpentane, thereby presenting
challenging structures for some DFT implementations