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    Point charge embedding for ONIOM excited states calculations

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    Biancardi_JCP_2016.pdf (8.248Mb)
    Issue Date
    2016-12-15
    Author
    Biancardi, Alessandro
    Barnes, Jeremy
    Caricato, Marco
    Publisher
    AIP Publishing
    Type
    Article
    Article Version
    Scholarly/refereed, publisher version
    Published Version
    http://aip.scitation.org/doi/10.1063/1.4972000
    Rights
    © The Authors 2016
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    Abstract
    Hybrid quantum mechanical methods can assist in the interpretation and prediction of the electronic spectra of large molecular structures. In this work, we study the performance of the ONIOM (Our own N-layered Integrated molecular Orbital molecular Mechanics) hybrid method for the calculation of transition energies and oscillator strengths by embedding the core region in a field of fixed point charges. These charges introduce polarization effects from the substituent groups to the core region. We test various charge definitions, with particular attention to the issue of overpolarization near the boundary between layers. To minimize this issue, we fit the charges on the electrostatic potential of the entire structure in the presence of the link atoms used to cap dangling bonds. We propose two constrained fitting strategies: one that produces an average set of charges common to both model system calculations, EE(L1), and one that produces two separate sets of embedding charges, EE(L2). The results from our tests show that indeed electronic embedding with constrained-fitted charges tends to improve the performance of ONIOM compared to non-embedded calculations. However, the EE(L2) charges work best for transition energies, and the EE(L1) charges work best for oscillator strengths. This may be an indication that fixed point charges do not have enough flexibility to adapt to each system, and other effects (e.g., polarization of the embedding field) may be necessary.
    URI
    http://hdl.handle.net/1808/25253
    DOI
    https://doi.org/10.1063/1.4972000
    Collections
    • Chemistry Scholarly Works [601]
    Citation
    Biancardi, A., Barnes, J., & Caricato, M. (2016). Point charge embedding for ONIOM excited states calculations. The Journal of Chemical Physics, 145(22), 224109. doi:10.1063/1.4972000

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    Lawrence, KS 66045
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    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

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