SO3 complexes with nitrogen containing ligands as the object of nuclear quadrupole interactions and density functional theory calculations

O. Kh Poleshchuk, V. Branchadell, A. V. Fateev, A. C. Legon

    Research output: Contribution to journalArticle

    2 Citations (Scopus)

    Abstract

    We have analyzed by means of DFT calculations of nitrogen nuclear quadrupole coupling constants of a range of SO3⋯B complexes (n aπ type in Mulliken notation) formed between molecules SO3 and Lewis bases B. The geometrical parameters, the rotational constants and the nitrogen nuclear quadrupole coupling constants obtained by these calculations substantially agree with the data from microwave spectroscopy in the gas phase. A good correlation is found between the calculated bond strengths of these complexes and the lengthening of the S-O bond. The NBO partitioning scheme and the stabilizing orbital interaction term suggest that there are excellent correlations between the charge transfer and the bond strength. From electron partitioning analyses and Klopman's approach, it follows that for the SO 3⋯B complexes the electrostatic contribution to the bonding is comparable to the covalent contribution.

    Original languageEnglish
    Pages (from-to)195-201
    Number of pages7
    JournalJournal of Molecular Structure: THEOCHEM
    Volume761
    Issue number1-3
    DOIs
    Publication statusPublished - 17 Mar 2006

    Fingerprint

    Density functional theory
    Nitrogen
    quadrupoles
    Microwave spectroscopy
    Lewis Bases
    density functional theory
    Ligands
    nitrogen
    ligands
    Microwaves
    Static Electricity
    Discrete Fourier transforms
    Charge transfer
    Electrostatics
    Spectrum Analysis
    Lewis base
    Gases
    interactions
    Electrons
    Molecules

    Keywords

    • DFT calculations
    • Electron partitioning analysis
    • Klopman's approach
    • Nitrogen nuclear quadrupole coupling constants
    • SO3⋯B complexes

    ASJC Scopus subject areas

    • Biochemistry
    • Condensed Matter Physics
    • Physical and Theoretical Chemistry

    Cite this

    SO3 complexes with nitrogen containing ligands as the object of nuclear quadrupole interactions and density functional theory calculations. / Poleshchuk, O. Kh; Branchadell, V.; Fateev, A. V.; Legon, A. C.

    In: Journal of Molecular Structure: THEOCHEM, Vol. 761, No. 1-3, 17.03.2006, p. 195-201.

    Research output: Contribution to journalArticle

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    AU - Poleshchuk, O. Kh

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    AU - Legon, A. C.

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    AB - We have analyzed by means of DFT calculations of nitrogen nuclear quadrupole coupling constants of a range of SO3⋯B complexes (n aπ type in Mulliken notation) formed between molecules SO3 and Lewis bases B. The geometrical parameters, the rotational constants and the nitrogen nuclear quadrupole coupling constants obtained by these calculations substantially agree with the data from microwave spectroscopy in the gas phase. A good correlation is found between the calculated bond strengths of these complexes and the lengthening of the S-O bond. The NBO partitioning scheme and the stabilizing orbital interaction term suggest that there are excellent correlations between the charge transfer and the bond strength. From electron partitioning analyses and Klopman's approach, it follows that for the SO 3⋯B complexes the electrostatic contribution to the bonding is comparable to the covalent contribution.

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