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

The Journal of Physical Chemistry. a
Tomoyasu Mani, David C Grills

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.

References

Jan 1, 1997·Annual Review of Physical Chemistry·G U Bublitz, S G Boxer
Jan 30, 2004·Journal of the American Chemical Society·Dmitrij Rappoport, Filipp Furche
Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
Sep 1, 2006·The Journal of Chemical Physics·Oleg A VydrovGustavo E Scuseria
Dec 28, 2006·The Journal of Chemical Physics·Oleg A Vydrov, Gustavo E Scuseria
Apr 28, 2007·The Journal of Chemical Physics·Oleg A VydrovJohn P Perdew
Nov 8, 2008·Physical Chemistry Chemical Physics : PCCP·Jeng-Da Chai, Martin Head-Gordon
Aug 27, 2009·The Journal of Physical Chemistry. B·Steven G Boxer
Jan 19, 2010·Accounts of Chemical Research·Marek Z ZgierskiEdward C Lim
Apr 29, 2010·Journal of the American Chemical Society·Shane ArdoGerald J Meyer
Mar 28, 2012·The Journal of Physical Chemistry. B·Nicholas M LevinsonSteven G Boxer
Jun 7, 2012·Journal of the American Chemical Society·Lori ZaikowskiJohn R Miller
Nov 26, 2013·The Journal of Physical Chemistry Letters·James M Marr, Zachary D Schultz
Jan 3, 2015·Journal of the American Chemical Society·Tomoyasu ManiJohn R Miller
Feb 24, 2015·Accounts of Chemical Research·Antonín VlčekStanislav Záliš
Mar 24, 2015·Accounts of Chemical Research·Stephen D Fried, Steven G Boxer
May 3, 2015·The Review of Scientific Instruments·David C GrillsJames F Wishart
Aug 4, 2015·Journal of the American Chemical Society·Tomoyasu ManiJohn R Miller
Jan 26, 2016·The Journal of Physical Chemistry. B·John HackTomoyasu Mani
Mar 5, 2016·Nature·Albert C AragonèsMichelle L Coote
Jun 22, 2016·Physical Chemistry Chemical Physics : PCCP·Bartosz BłasiakMinhaeng Cho
Sep 30, 2016·The Journal of Physical Chemistry Letters·Arthur E BraggTimothy Magnanelli
Jan 10, 2017·Accounts of Chemical Research·Bogdan DerekaEric Vauthey
Feb 10, 2017·Physical Chemistry Chemical Physics : PCCP·Hao WangZachary D Schultz
Jul 6, 2017·The Journal of Physical Chemistry. B·Tomoyasu Mani, David C Grills

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.