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

Tomoyasu Mani, David Grills

Research output: Contribution to journalArticle

3 Citations (Scopus)

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, 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
Volume122
Issue number37
DOIs
Publication statusPublished - Sep 20 2018

Fingerprint

Nitriles
nitriles
Stark effect
Charge transfer
charge transfer
Electric fields
vibration
electric fields
Electrons
Molecules
electrons
polarization (charge separation)
molecules
polarity
Screening
screening
sensitivity
benzonitrile

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles. / Mani, Tomoyasu; Grills, David.

In: Journal of Physical Chemistry A, Vol. 122, No. 37, 20.09.2018, p. 7293-7300.

Research output: Contribution to journalArticle

@article{14981f4781c4426382d6df89cb56025a,
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, 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.",
author = "Tomoyasu Mani and David Grills",
year = "2018",
month = "9",
day = "20",
doi = "10.1021/acs.jpca.8b08025",
language = "English",
volume = "122",
pages = "7293--7300",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "37",

}

TY - JOUR

T1 - Nitrile Vibration Reports Induced Electric Field and Delocalization of Electron in the Charge-Transfer State of Aryl Nitriles

AU - Mani, Tomoyasu

AU - Grills, David

PY - 2018/9/20

Y1 - 2018/9/20

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85053766439&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85053766439&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.8b08025

DO - 10.1021/acs.jpca.8b08025

M3 - Article

AN - SCOPUS:85053766439

VL - 122

SP - 7293

EP - 7300

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 37

ER -