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An IEF-PCM study of solvent effects on the Faraday \({\mathcal{B}}\) term of MCD

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Abstract

We present the first theoretical investigation of solvent effects on the Faraday \({\mathcal{B}}\) term of magnetic circular dichroism (MCD) at the density–functional level of theory. In our model, the solvent is described by the polarizable continuum model in its integral-equation formulation. We present the extensions required for including electron correlation effects using density–functional theory (DFT) as well as the necessary extensions for including the effects of a dielectric continuum. The new code is applied to the study of the Faraday \({\mathcal{B}}\) term of MCD in a series of benzoquinones. It is demonstrated that electron correlation effects, as described by DFT, are essential in order to recover the experimentally observed signs of the \({\mathcal{B}}\) term. Dielectric continuum effects increase, in general, the magnitude of the \({\mathcal{B}}\) term, leading to an overestimation of the experimental observations in most cases.

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Authors and Affiliations

  1. Department of Chemistry, University of Tromsø, 9037, Tromsø, Norway

    Harald Solheim, Luca Frediani & Kenneth Ruud

  2. Dipartimento di Scienze Chimiche, Università di Trieste, Via L. Giorgieri 1, 34127, Trieste, Italy

    Sonia Coriani

Authors
  1. Harald Solheim
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  2. Luca Frediani
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  3. Kenneth Ruud
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  4. Sonia Coriani
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Correspondence to Kenneth Ruud.

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Solheim, H., Frediani, L., Ruud, K. et al. An IEF-PCM study of solvent effects on the Faraday \({\mathcal{B}}\) term of MCD. Theor Chem Account 119, 231–244 (2008). https://doi.org/10.1007/s00214-006-0235-9

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  • DOI: https://doi.org/10.1007/s00214-006-0235-9

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