A concise set of large, symmetric molecules for evaluation of modern computational methods

Journal of Physical Chemistry A

Volumn 105, Issue 39, 2001, Pages 9040-9048

  Pascal Jr , Robert A ^a  

^a PRINCETON UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

HYBRID DENSITY FUNCTIONAL (HDFT) METHODS;

COMPUTATIONAL METHODS; MOLECULAR STRUCTURE; OPTIMIZATION; PROBABILITY DENSITY FUNCTION; QUANTUM THEORY; X RAY ANALYSIS;

AROMATIC COMPOUNDS;

EID: 0035807658     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp011482j     Document Type: Article

References (63)

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32. My own interest in these computational problems began with the observation that HDFT calculations systematically overestimated the bond distances in the polycyclic aromatic hydrocarbon hexabenzotriphenylene, so that the calculated diameter of this large, propeller-shaped molecule (C42H2-0 was fully 0.1 A greater than that of an accurate, low-temperature X-ray structure.24 Low-level Hartree-Fock (HF) calculations gave better overall geometries than the HDFT methods for the simple reason that the HF bond length errors were randomly dispersed about the experimental values. The overestimation of bond lengths by HDFT methods is hardly unknown,25'26 but certainly unadvertised.
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37. Another virtue of high-symmetry structures is that the data may be of better quality. Although I am unaware of any studies establishing such a correlation for small-molecule determinations, Dickerson and coworkers29 have found it to be true for macromolecules, noting that among all the available self-complementary B-DNA crystal structure analyses, those crystals exhibiting the highest resolution are the ones that minimally perturb the intrinsic 2-fold internal symmetry of the molecule. Highest resolution ... is obtained in the monoclinic space group C2, where the molecular symmetry coincides with a true crystallographic 2-fold axis... Where this is forbidden by anisotropic crystal packing, a price is paid in terms of increased disorder within the crystal structure and lower resolution.
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