Density functional studies on the reagents Me3AsX2 (where X = F, Cl, Br and I) in the gas phase and in solution

Stephen M. Godfrey, Alan Hinchliffe

    Research output: Contribution to journalArticlepeer-review


    We report Density Functional Studies at the B3LYP level of theory (with 6-311++g(3d, 2p) or DGDZVP basis sets as appropriate) for the title reagents. We located three minima for each X (two for X = F). These correspond to an ion pair (IP), a trigonal structure (TR) and a spoke-shaped charge transfer complex (CT). Our calculations suggest that there is no stable gas-phase CT complex for X = F. The IP structure for X = F is close to C2v symmetry (but with a distinct Mulliken charge difference on the F atoms). The three representative solvents cyclohexane, dichloromethane and water were modelled using the Polarized Continuum Model (PCM). The most stable gas-phase structure is TR for all X apart from X = I where TR ≈ CT. The TR structure is the most stable for all three solvents modelled except when X = I, when TR ≈ CT for solvents with low relative permittivity. The CT structure is favoured in this case as the relative permittivity increases. © 2006 Elsevier B.V. All rights reserved.
    Original languageEnglish
    Pages (from-to)89-94
    Number of pages5
    JournalJournal of Molecular Structure: THEOCHEM
    Issue number1-3
    Publication statusPublished - 6 Nov 2006


    • B3LYP
    • Charge transfer complex
    • Density functional theory
    • Dibromine
    • Dichlorine
    • Difluorine
    • Diiodine
    • PCM
    • Solvation studies
    • Trimethylarsine


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