Experimental Exploration of the Mulliken鈭扝ush Relationship for Intramolecular Electron Transfer Reactions

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• 作者：Tamal Mukherjee ; Naoki Ito ; Ian R. Gould
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：March 17, 2011
• 年：2011
• 卷：115
• 期：10
• 页码：1837-1843
• 全文大小：835K
• 年卷期：v.115,no.10(March 17, 2011)
• ISSN：1520-5215

文摘

The Mulliken鈭扝ush (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.