Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions

Tamal Mukherjee, Naoki Ito, Ian Gould

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Abstract

The Mulliken-Hush (M-H) relationship provides the critical link between optical and thermal electron transfer processes, and yet very little direct experimental support for its applicability has been provided. Dicyanovinylazaadamantane (DCVA) represents a simple two-state (neutral/charge-transfer) intramolecular electron transfer system that exhibits charge-transfer absorption and emission spectra that are readily measurable in solvents with a wide range of polarities. In this regard it represents an ideal model system for studying the factors that control both optical charge separation (absorption) and recombination (emission) processes in solution. Here we explore the applicability of the M-H relation to quantitative descriptions of the optical charge-transfer processes in DCVA. For DCVA, the measured radiative rate constants exhibit a linear dependence on transition energy, and transition dipole moments exhibit an inverse dependence on transition energy, consistent with the M-H relationship.

Original languageEnglish (US)
Pages (from-to)1837-1843
Number of pages7
JournalJournal of Physical Chemistry A
Volume115
Issue number10
DOIs
Publication statusPublished - Mar 17 2011

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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