Theory of solvatochromic shifts in nonpolar solvents reveals a new spectroscopic rule

Thomas Renger, Bernhard Grundkötter, Mohamed El Amine Madjet, Frank Müh

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

An expression of unexpected simplicity is derived for the shift in optical transition energies of solute molecules in nonpolar solvents. The expression reveals a new spectroscopic rule that says: The higher the excited state of the solute, the larger the solvatochromic red shift. A puzzle formulated >50 years ago by Bayliss is solved. Bayliss, based on arguments from classical physics, assumed that the shift scales with the oscillator strength of the solute transition, but noted strong quantitative deviations from this rule in experiments. As the present expression shows, the shift does not depend on the oscillator strength of the transition, but reflects the change in dispersive solute-solvent interactions between the ground and excited states of the solute, that are determined by the anisotropy of intramolecular electron correlation. The theory is applied to explain the solvatochromic shifts of the two lowest electronic excitations of bacteriochlorophyll a and bacteriopheophytin a.

Original languageEnglish
Pages (from-to)13235-13240
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume105
Issue number36
DOIs
Publication statusPublished - 9 Sep 2008

Keywords

  • Dispersive interactions
  • Extended dipole
  • Oscillator strength sum rule
  • Solvation energy
  • Transition density

ASJC Scopus subject areas

  • General

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