DECAT - Artigos publicados em periódicos

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Browsing DECAT - Artigos publicados em periódicos by Subject "Ab initio methods"

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    An ab initio study of the C2H2 HF, C2H(CH3) HF and C2(CH3)2 HF hydrogen-bonded complexes.
    (2006) Ramos, Mozart Neves; Lopes, Kelson Carvalho; Silva, Washington Luís Vieira da; Figueirêdo, Alessandra Marcone Tavares Alves de; Castrini, Fátima Aparecida; Monte, Silmar Andrade do; Ventura, Elizete; Araújo, Regiane de Cássia Maritan Ugulino de
    MP2/6-31++G** and B3LYP/6-31++G** ab initio molecular orbital calculations have been performed in order to obtain molecular geometries, binding energies and vibrational properties of the C2H2 HF, C2H(CH3) HF and C2(CH3)2 HF H-bonded complexes. As expected, the more pronounced effects on the structural properties of the isolated molecules due to complexation was verified for the C C and H F bond lengths, which are directly involved in the H-bond formation. These bond distances increased after complexation. BSSE uncorrected B3LYP binding energies are always lower than the corresponding MP2 values. However, the opposite trend has been verified after BSSE correction by the counterpoise method since it is much lower at B3LYP than at MP2 level. The binding energies for these complexes as well as for the HF acid submolecule modes (the HF stretching and vibrational frequency modes) showed an increasing hydrogen-bonding strength with increasing methyl substitution. The splitting in the HF in-plane and out-of-plane bending modes reflects the anisotropy in the hydrogen-bonding interaction with the _ system of the C C bond. The H F stretching frequency is shifted downward after complexation and it increases with the methyl substitution. The IR intensities of the HF acid submolecule fundamentals are adequately interpreted through the atomic polar tensor of the hydrogen atom using the charge–charge flux-overlap model. The skeletal stretching modes of the Alkyne submolecule are decreased in the complex. The new vibrational modes arising from complexation show several interesting features.