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dc.contributor.author
Iramain, Maximiliano Alberto
dc.contributor.author
Castillo, María V.
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Davies, Lilian Emilia
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Manzur, Maria Eugenia
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Brandan, Silvia Antonia
dc.date.available
2020-12-29T15:14:03Z
dc.date.issued
2020-01
dc.identifier.citation
Iramain, Maximiliano Alberto; Castillo, María V.; Davies, Lilian Emilia; Manzur, Maria Eugenia; Brandan, Silvia Antonia; Structural and SQMFF study of potent insecticide 4′,4′-DDT combining the FT-IR and FT-Raman spectra with DFT calculations; Elsevier Science; Journal of Molecular Structure; 1199; 1-2020; 126964-126974
dc.identifier.issn
0022-2860
dc.identifier.uri
http://hdl.handle.net/11336/121272
dc.description.abstract
The experimental FT-IR and FT-Raman spectra in the solid state have been employed to vibrationally characterize the potent insecticide dichlorodiphenyltrichloroethane (4′,4′-DDT). The complete vibrational assignments of 4′,4′-DDT in gas phase and in acetone and diethyl-ether were performed combining hybrid B3LYP/6-31G* and B3LYP/6–311++G** calculations with the internal coordinates, the scaled quantum mechanical force field (SQMFF) methodology and the experimental spectra. Here, the molecular structures of 4′,4′-DDT were theoretically determined in gas phase and in acetone and diethyl-ether solutions by using those two methods. The self-consistent reaction field (SCRF) method and the integral equation formalism variant polarised continuum model (IEFPCM) model were employed to study the properties in solution while the solvation energies were predicted by using the solvation model. The B3LYP/6–311++G** calculations show higher solvation energy in the solvent with lower permittivity, diethyl-ether. A clear and direct correlation was found with both basis sets between solvation energy and dipole moment for those two solvents. NBO studies clearly show that dichlorodiphenyl groups confer to 4,4′-DDT higher stability than the trichloroethyl group due to the fact that the lone pairs of Cl21 and Cl22 atoms present the n→π* transitions while the AIM study shows the participation of trichloroethyl group in halogen bonds clearly justifying the stability of 4′,4′-DDT in the three media and with both basis sets. The MK and NPA charges evidence different behaviors in both media and with both basis sets. The frontier orbitals show that the reactivity of 4,4′-DDT strongly depends on the basis set while it is more reactive than dieldrin, hexachlorobenzene and saxitoxin but 3,3′,4,4′-tetrachloroazobenzene, 3,3′,4,4′ tetrachloroazoxybenzene, CN− and CO species present higher reactivity than 4,4′-DDT. The number of Cl atoms could justify the differences observed in the nucleophilicity indexes of 4,4′-DDT, dieldrin, hexachlorobenzene, 3,3′,4,4′-tetrachloroazobenzene and 3,3′,4,4′ tetrachloroazoxybenzene.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Elsevier Science
dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
DESCRIPTOR PROPERTIES
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DFT CALCULATIONS
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DICHLORODIPHENYLTRICHLOROETHANE
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MOLECULAR STRUCTURE
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VIBRATIONAL SPECTRA
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Otras Ciencias Químicas
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Ciencias Químicas
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CIENCIAS NATURALES Y EXACTAS
dc.title
Structural and SQMFF study of potent insecticide 4′,4′-DDT combining the FT-IR and FT-Raman spectra with DFT calculations
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2020-12-10T13:31:35Z
dc.journal.volume
1199
dc.journal.pagination
126964-126974
dc.journal.pais
Países Bajos
dc.journal.ciudad
Amsterdam
dc.description.fil
Fil: Iramain, Maximiliano Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia; Argentina
dc.description.fil
Fil: Castillo, María V.. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia; Argentina
dc.description.fil
Fil: Davies, Lilian Emilia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Investigaciones para la Industria Química. Universidad Nacional de Salta. Facultad de Ingeniería. Instituto de Investigaciones para la Industria Química; Argentina. Universidad Nacional de Salta. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Química Orgánica; Argentina
dc.description.fil
Fil: Manzur, Maria Eugenia. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Inorgánica; Argentina
dc.description.fil
Fil: Brandan, Silvia Antonia. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Inorgánica; Argentina
dc.journal.title
Journal of Molecular Structure
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/https://doi.org/10.1016/j.molstruc.2019.126964
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0022286019310555
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