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Title: Dynamics of an excess hole in the 1-methyl-1-butyl-pyrrolidinium dicyanamide ionic-liquid

Abstract

In a set of recent publications we explored for selected ionic liquids the early stages of excess charge localization and reactivity relevant both to electrochemical and radiation chemistry processes. W explored the dynamics of an excess electron in 1-methyl-1-butyl-pyrrolidinium dicyanamide. When electrons are produced from an ionic liquid, the more elusive hole species are also generated. Depending on the nature of cations and anions and the relative alignment of their electronic states in the condensed phase, the very early hole species can nominally be neutral radicals—if the electron is generated from anions—or doubly charged radical cations if their origin is from cations. However, in reality early excess charge localization is more complex and often involves more than one ion. The dynamics and the transient spectroscopy of the hole are the main objects of this study. We find that in the case of 1-methyl-1-butyl-pyrrolidinium dicyanamide, it is the anions that can most easily lose an electron becoming radical species, and that hole localization is mostly on anionic nitrogen. We also find that the driving force for localization of an excess hole appears to be smaller than that for an excess electron in 1-methyl-1-butyl-pyrrolidinium dicyanamide. The early transient hole species can absorbmore » light in the visible, ultraviolet, and near infrared regions, and we are able to identify the type of states being connected by these transitions.« less

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Univ. of Iowa, Iowa City, IA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Rutgers Univ., Piscataway, NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1540141
Alternate Identifier(s):
OSTI ID: 1422663
Grant/Contract Number:  
SC0001780
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Physics

Citation Formats

Wu, Fei, Xu, Changhui, and Margulis, Claudio J. Dynamics of an excess hole in the 1-methyl-1-butyl-pyrrolidinium dicyanamide ionic-liquid. United States: N. p., 2018. Web. doi:10.1063/1.5009940.
Wu, Fei, Xu, Changhui, & Margulis, Claudio J. Dynamics of an excess hole in the 1-methyl-1-butyl-pyrrolidinium dicyanamide ionic-liquid. United States. doi:10.1063/1.5009940.
Wu, Fei, Xu, Changhui, and Margulis, Claudio J. Mon . "Dynamics of an excess hole in the 1-methyl-1-butyl-pyrrolidinium dicyanamide ionic-liquid". United States. doi:10.1063/1.5009940. https://www.osti.gov/servlets/purl/1540141.
@article{osti_1540141,
title = {Dynamics of an excess hole in the 1-methyl-1-butyl-pyrrolidinium dicyanamide ionic-liquid},
author = {Wu, Fei and Xu, Changhui and Margulis, Claudio J.},
abstractNote = {In a set of recent publications we explored for selected ionic liquids the early stages of excess charge localization and reactivity relevant both to electrochemical and radiation chemistry processes. W explored the dynamics of an excess electron in 1-methyl-1-butyl-pyrrolidinium dicyanamide. When electrons are produced from an ionic liquid, the more elusive hole species are also generated. Depending on the nature of cations and anions and the relative alignment of their electronic states in the condensed phase, the very early hole species can nominally be neutral radicals—if the electron is generated from anions—or doubly charged radical cations if their origin is from cations. However, in reality early excess charge localization is more complex and often involves more than one ion. The dynamics and the transient spectroscopy of the hole are the main objects of this study. We find that in the case of 1-methyl-1-butyl-pyrrolidinium dicyanamide, it is the anions that can most easily lose an electron becoming radical species, and that hole localization is mostly on anionic nitrogen. We also find that the driving force for localization of an excess hole appears to be smaller than that for an excess electron in 1-methyl-1-butyl-pyrrolidinium dicyanamide. The early transient hole species can absorb light in the visible, ultraviolet, and near infrared regions, and we are able to identify the type of states being connected by these transitions.},
doi = {10.1063/1.5009940},
journal = {Journal of Chemical Physics},
number = 19,
volume = 148,
place = {United States},
year = {2018},
month = {5}
}

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