How solvent controls electronic energy transfer and light harvesting: Toward a quantum-mechanical description of reaction field and screening effects

Carles Curutchet, Gregory D. Scholes, Benedetta Mennucci, Roberto Cammi

Research output: Contribution to journalArticle

94 Scopus citations

Abstract

This paper presents a quantum-mechanical study of electronic energy transfer (EET) coupling on over 100 pairs of chromophores taken from photosynthetic light-harvesting antenna proteins. Solvation effects due to the protein, intrinsic waters, and surrounding medium are analyzed in terms of screening and reaction field contributions using a model developed recently that combines a linear response approach with the polarizable continuum model (PCM). We find that the screening of EET interactions is quite insensitive to the quantummechanical treatment adopted. In contrast, it is greatly dependent on the geometrical details (distance, shape, and orientation) of the chromophore pair considered. We demonstrate that implicit (reaction field) as well as screening effects are dictated mainly by the optical dielectric properties of the host medium, while the effect of the static properties is substantially less important. The empirical distance-dependent screening function we proposed in a recent letter (Scholes, G. D.; Curutchet, C.; Mennucci, B.; Cammi, R.; Tomasi, J. J. Phys. Chem. B 2007, 111, 6978-6982) is analyzed and compared to other commonly used screening factors. In addition, we show that implicit medium effects on the coupling, resulting from changes in the transition densities upon solvation, are strongly dependent on the particular system considered, thus preventing the possibility of defining a general empirical expression for such an effect.

Original languageEnglish (US)
Pages (from-to)13253-13265
Number of pages13
JournalJournal of Physical Chemistry B
Volume111
Issue number46
DOIs
StatePublished - Nov 22 2007
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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