These tools will no longer be maintained as of December 31, 2024. Archived website can be found here. PubMed4Hh GitHub repository can be found here. Contact NLM Customer Service if you have questions.


Pubmed for Handhelds

PUBMED FOR HANDHELDS

Search MEDLINE/PubMed

  • Title: A Gaussian-3X prediction on the enthalpies of formation of chlorinated phenols and dibenzo-p-dioxins.
    Author: Wang L, Heard DE, Pilling MJ, Seakins P.
    Journal: J Phys Chem A; 2008 Feb 28; 112(8):1832-40. PubMed ID: 18232671.
    Abstract:
    The standard gas-phase enthalpies of formation of chlorinated benzenes, phenols and dibenzo-p-dioxins have been predicted using G3X and/or G3XMP2 model chemistries coupled with isodesmic reactions and compared to the previous theoretical and experimental values. A set of values for chlorinated benzenes are first suggested based on experimental measurements and the closed agreed G3X calculations with different isodesmic reactions. The results on polychlorinated dibenzo-p-dioxins (PCDDs) show a large difference between G3XMP2 and previous experimental measurements and predictions using group additivity methods, semiempirical quantum chemistry, and DFT calculations, especially for highly chlorinated species. Using the well-balanced isodesmic reactions (IR3 and IR5), the discrepancies between G3XMP2 and DFT predictions on PCDDs can be reduced to within 16 kJ/mol. The relative stability of PCDD isomers can be rationalized by the positional interactions, and the overestimation by DFT with less balanced isodesmic reactions is due to the overestimation of the ortho-Cl-Cl repulsive interactions when comparing with G3XMP2. Our calculations suggest further experimental measurements, especially on highly chlorinated phenols and PCDDs.
    [Abstract] [Full Text] [Related] [New Search]