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

Abstract

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 in this paper, 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. Finally, 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.

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of Connecticut, Storrs, CT (United States). Department of Chemistry
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1473657
Report Number(s):
BNL-209069-2018-JAAM
Journal ID: ISSN 1089-5639
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 37; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Mani, Tomoyasu, and Grills, David C. Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b08025.
Mani, Tomoyasu, & Grills, David C. Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles. United States. https://doi.org/10.1021/acs.jpca.8b08025
Mani, Tomoyasu, and Grills, David C. 2018. "Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles". United States. https://doi.org/10.1021/acs.jpca.8b08025. https://www.osti.gov/servlets/purl/1473657.
@article{osti_1473657,
title = {Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles},
author = {Mani, Tomoyasu and Grills, David C.},
abstractNote = {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 in this paper, 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. Finally, 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.},
doi = {10.1021/acs.jpca.8b08025},
url = {https://www.osti.gov/biblio/1473657}, journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 37,
volume = 122,
place = {United States},
year = {Fri Aug 24 00:00:00 EDT 2018},
month = {Fri Aug 24 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 8 works
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Works referencing / citing this record:

Structural origins of the electronic properties of materials via time-resolved infrared spectroscopy
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