Theoretical Chemistry Accounts

, Volume 119, Issue 1–3, pp 231–244 | Cite as

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

  • Harald Solheim
  • Luca Frediani
  • Kenneth Ruud
  • Sonia Coriani
Regular Article

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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Copyright information

© Springer-Verlag 2007

Authors and Affiliations

  • Harald Solheim
    • 1
  • Luca Frediani
    • 1
  • Kenneth Ruud
    • 1
  • Sonia Coriani
    • 2
  1. 1.Department of ChemistryUniversity of TromsøTromsøNorway
  2. 2.Dipartimento di Scienze ChimicheUniversità di TriesteTriesteItaly

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