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Type: Artigo de periódico
Title: Spurious Phosphorus Pyramidalization Induced By Some Dft Functionals
Author: Pupim
Carina F.; Morgon
Nelson H.; Lopez-Castillo
Abstract: The molecular geometries of boraphosphabenzene (BP-benzene) and boron phosphorus coronene (BP-coronene) can be misinterpreted when they are obtained from density functional theory (DFT) calculations. In this study, we found that some exchange-correlation (XC) functionals yielded a distorted geometry of the above molecules when P atoms are present in their resonance structures. This phosphorus pyramidalization may be due to spurious errors caused by using these functionals. To verify this behavior, the electronic structures of BP-benzene and BP-coronene were studied using sixteen functionals (B3LYP, B97D, BHLYP, BP96, PBE, PBE0, PWLDA, Slater-Dirac-exchange, TPSS, M05, M06, M062X, M08HX, M11, wB97 and wB97X-D) with the SVP or TZVPP basis sets. The calculations were carried out using the TURBOMOLE and GAMESS programs. The geometry optimization calculations were carried out for each functional using both of the basis sets. Two different initial geometries, plane (D-3h symmetry) and distorted (C-1 symmetry) were considered. The optimized geometries of the BP-systems obtained at the MP2/TZVPP and CC2/TZVPP levels of theory exhibited D-3h symmetry. These calculations were used as a reference and compared with those obtained from DFT. The optimized geometries obtained from DFT were found to exhibit C-1 symmetry for the majority of the XC functionals.
Subject: Main-group Thermochemistry
Zeta Valence Quality
Noncovalent Interactions
Density Functionals
Country: SAO PAULO
Rights: fechado
Identifier DOI: 10.5935/0103-5053.20150138
Date Issue: 2015
Appears in Collections:Unicamp - Artigos e Outros Documentos

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