Accounting for non-optimal interactions in molecular recognition: A study of ion-π complexes using a QM/MM model with a dipole-polarisable MM region

Qiantao Wang, Richard A. Bryce

    Research output: Contribution to journalArticlepeer-review

    Abstract

    For a quantitative understanding of molecular structure, interaction and dynamics, accurate modelling of the energetics of both near-equilibrium and less optimal contacts is important. In this work, we explore the potential energy surfaces of representative ion-π complexes. We examine the performance of a semi-empirical QM/MM approach and the corresponding QM/MMpol model, where inducible point dipoles are additionally employed in the MM region. The predicted potential energy surfaces of cation-benzene complexes are improved by inclusion of explicit MM polarisation of the π-molecule. For cation-formamide complexes, inducible dipoles appreciably improve energetic estimates at geometries forming non-optimal interactions. Energetic component analysis suggests that the implicit MM polarisation of the fixed charge QM/MM model mirrors the behaviour of the QM/MMpol dipole model for the energetics of near-equilibrium conformations. However, for complexes at less optimal orientations, the QM/MM model exhibits higher errors than the QM/MMpol approach, being unable to capture orientation-dependent variations in polarisation energy. © the Owner Societies 2011.
    Original languageEnglish
    Pages (from-to)19401-19408
    Number of pages7
    JournalPhysical Chemistry Chemical Physics
    Volume13
    Issue number43
    DOIs
    Publication statusPublished - 21 Nov 2011

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