Ab initio study of weakly bound halogen complexes: RXa <-PH3

Ab initio study of weakly bound halogen complexes: RXa <-PH3

Author Georg, Herbert C. Google Scholar
Fileti, Eudes E. Autor UNIFESP Google Scholar
Malaspina, Thaciana Autor UNIFESP Google Scholar
Institution Universidade Federal de São Paulo (UNIFESP)
Universidade Federal de Goiás (UFG)
Abstract Ab initio calculations were employed to study the role of ipso carbon hybridization in halogenated compounds RX (R = methyl, phenyl, acetyl, H and X = F, Cl, Br and I) and its interaction with a phosphorus atom, as occurs in the halogen bonded complex type RXa <-PH3. the analysis was performed using ab initio MP2, MP4 and CCSD(T) methods. Systematic energy analysis found that the interaction energies are in the range -4.14 to -11.92 kJ mol(-1) (at MP2 level without ZPE correction). Effects of electronic correlation levels were evaluated at MP4 and CCSD(T) levels and a reduction of up to 27 % in interaction energy obtained in MP2 was observed. Analysis of the electrostatic maps confirms that the PhCla <-PH3 and all MeXa <-PH3 complexes are unstable. NBO analysis suggested that the charge transfer between the moieties is bigger when using iodine than bromine and chlorine. the electrical properties of these complexes (dipole and polarizability) were determined and the most important observed aspect was the systematic increase at the dipole polarizability, given by the interaction polarizability. This increase is in the range of 0.7-6.7 u.a. (about 3-7 %).
Keywords Abinitio calculation
Halogen bonded complex
Molecular property
Interaction energy
Language English
Sponsor Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Date 2013-01-01
Published in Journal of Molecular Modeling. New York: Springer, v. 19, n. 1, p. 329-336, 2013.
ISSN 1610-2940 (Sherpa/Romeo, impact factor)
Publisher Springer
Extent 329-336
Origin http://dx.doi.org/10.1007/s00894-012-1551-8
Access rights Closed access
Type Article
Web of Science ID WOS:000313077100031
URI http://repositorio.unifesp.br/handle/11600/35781

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