Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects

The Journal of Physical Chemistry. B
John HackTomoyasu Mani

Abstract

Ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N) infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In ...Continue Reading

References

Apr 1, 2003·Journal of Computational Chemistry·Maurizio CossiVincenzo Barone
May 13, 2004·Chemical Reviews·George W GokelMichelle E Weber
Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
Nov 10, 2006·Chemical Reviews·Yizhak Marcus, Glenn Hefter
Apr 28, 2007·The Journal of Chemical Physics·Oleg A VydrovJohn P Perdew
Aug 27, 2009·The Journal of Physical Chemistry. B·Steven G Boxer
Nov 12, 2010·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Kwang-Hee ParkMinhaeng Cho
Mar 28, 2012·The Journal of Physical Chemistry. B·Nicholas M LevinsonSteven G Boxer
Feb 13, 2013·The Journal of Physical Chemistry. B·Shiguo ZhangYouquan Deng
Jun 14, 2014·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Koichi FuminoRalf Ludwig
Sep 19, 2014·The Journal of Physical Chemistry. a·Tomoyasu Mani, John R Miller
Jan 3, 2015·Journal of the American Chemical Society·Tomoyasu ManiJohn R Miller
Jan 16, 2015·The Journal of Physical Chemistry. B·Kamila K MentelLuis G Arnaut
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
May 1, 2014·The Journal of Physical Chemistry Letters·Zhe RenSean Garrett-Roe

❮ Previous
Next ❯

Citations

Jul 6, 2017·The Journal of Physical Chemistry. B·Tomoyasu Mani, David C Grills
Apr 16, 2019·Physical Chemistry Chemical Physics : PCCP·Xiao YangXiaoning Yang
Sep 20, 2019·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Lei ZhangGuo-Hong Tao
Feb 10, 2017·Physical Chemistry Chemical Physics : PCCP·Hao WangZachary D Schultz

❮ 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.

© 2021 Meta ULC. All rights reserved