Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles

Tomoyasu Mani, David Grills

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4 Citations (Scopus)


An electric field is created upon photoinduced charge separation in electron donor-acceptor (D-A) molecules. The photophysics of a prototypical D-A molecule, 4-(dimethylamino)-benzonitrile (DMABN), has been under extensive investigation for decades. Here, by using the framework of the vibrational Stark effect (VSE), we show that the nitrile vibration quantifies a significant induced electric field in the intramolecular charge-transfer state of DMABN. We further demonstrate that such a phenomenon can be observed in a structurally similar aryl nitrile and that the VSE depends on solvent polarity due to dielectric screening. Our current work shows how the superb sensitivity of the nitrile vibration can be used to identify the nature of electron delocalization and quantify the induced electric field in photoinduced charge transfer processes.

Original languageEnglish
Pages (from-to)7293-7300
Number of pages8
JournalJournal of Physical Chemistry A
Issue number37
Publication statusPublished - Sep 20 2018


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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