Measurements of the complete solvation response in ionic liquids

Sergei Arzhantsev, Hui Jin, Gary A. Baker, Mark Maroncelli

Research output: Contribution to journalArticle

200 Citations (Scopus)

Abstract

Dynamic Stokes shift measurements of the solvatochromic probe trans-4-dimethylamino-4′-cyanostilbene were used to measure the solvation response of five imidazolium and one pyrrolidinium ionic liquid at 25°C. The Kerr-gated emission and time-correlated single-photon-counting techniques were used to measure spectral dynamics occurring over the time ranges of 100 fs-200 ps and 50 ps-5 ns, respectively, and a combination of data sets from these two techniques enabled observation of the complete solvation response. Observed response functions were found to be biphasic, consisting of a sub-picosecond component of modest (10-20%) amplitude and a dominant slower component relaxing over times of a few picoseconds to several nanoseconds. The faster component could be correlated to inertial characteristics of the constituent ions, and the slower component to solvent viscosity. Dielectric continuum calculations of the sort previously used to predict solvation dynamics in dipolar liquids were shown to work poorly for predicting the response in these ionic liquids.

Original languageEnglish (US)
Pages (from-to)4978-4989
Number of pages12
JournalJournal of Physical Chemistry B
Volume111
Issue number18
DOIs
StatePublished - May 10 2007

Fingerprint

Ionic Liquids
Solvation
Ionic liquids
solvation
liquids
Photons
Viscosity
Ions
counting
Liquids
viscosity
continuums
probes
shift
photons
ions

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Arzhantsev, Sergei ; Jin, Hui ; Baker, Gary A. ; Maroncelli, Mark. / Measurements of the complete solvation response in ionic liquids. In: Journal of Physical Chemistry B. 2007 ; Vol. 111, No. 18. pp. 4978-4989.
@article{b927550d2b8c42028a3cced072743240,
title = "Measurements of the complete solvation response in ionic liquids",
abstract = "Dynamic Stokes shift measurements of the solvatochromic probe trans-4-dimethylamino-4′-cyanostilbene were used to measure the solvation response of five imidazolium and one pyrrolidinium ionic liquid at 25°C. The Kerr-gated emission and time-correlated single-photon-counting techniques were used to measure spectral dynamics occurring over the time ranges of 100 fs-200 ps and 50 ps-5 ns, respectively, and a combination of data sets from these two techniques enabled observation of the complete solvation response. Observed response functions were found to be biphasic, consisting of a sub-picosecond component of modest (10-20{\%}) amplitude and a dominant slower component relaxing over times of a few picoseconds to several nanoseconds. The faster component could be correlated to inertial characteristics of the constituent ions, and the slower component to solvent viscosity. Dielectric continuum calculations of the sort previously used to predict solvation dynamics in dipolar liquids were shown to work poorly for predicting the response in these ionic liquids.",
author = "Sergei Arzhantsev and Hui Jin and Baker, {Gary A.} and Mark Maroncelli",
year = "2007",
month = "5",
day = "10",
doi = "10.1021/jp067273m",
language = "English (US)",
volume = "111",
pages = "4978--4989",
journal = "Journal of Physical Chemistry B",
issn = "1520-6106",
number = "18",

}

Measurements of the complete solvation response in ionic liquids. / Arzhantsev, Sergei; Jin, Hui; Baker, Gary A.; Maroncelli, Mark.

In: Journal of Physical Chemistry B, Vol. 111, No. 18, 10.05.2007, p. 4978-4989.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Measurements of the complete solvation response in ionic liquids

AU - Arzhantsev, Sergei

AU - Jin, Hui

AU - Baker, Gary A.

AU - Maroncelli, Mark

PY - 2007/5/10

Y1 - 2007/5/10

N2 - Dynamic Stokes shift measurements of the solvatochromic probe trans-4-dimethylamino-4′-cyanostilbene were used to measure the solvation response of five imidazolium and one pyrrolidinium ionic liquid at 25°C. The Kerr-gated emission and time-correlated single-photon-counting techniques were used to measure spectral dynamics occurring over the time ranges of 100 fs-200 ps and 50 ps-5 ns, respectively, and a combination of data sets from these two techniques enabled observation of the complete solvation response. Observed response functions were found to be biphasic, consisting of a sub-picosecond component of modest (10-20%) amplitude and a dominant slower component relaxing over times of a few picoseconds to several nanoseconds. The faster component could be correlated to inertial characteristics of the constituent ions, and the slower component to solvent viscosity. Dielectric continuum calculations of the sort previously used to predict solvation dynamics in dipolar liquids were shown to work poorly for predicting the response in these ionic liquids.

AB - Dynamic Stokes shift measurements of the solvatochromic probe trans-4-dimethylamino-4′-cyanostilbene were used to measure the solvation response of five imidazolium and one pyrrolidinium ionic liquid at 25°C. The Kerr-gated emission and time-correlated single-photon-counting techniques were used to measure spectral dynamics occurring over the time ranges of 100 fs-200 ps and 50 ps-5 ns, respectively, and a combination of data sets from these two techniques enabled observation of the complete solvation response. Observed response functions were found to be biphasic, consisting of a sub-picosecond component of modest (10-20%) amplitude and a dominant slower component relaxing over times of a few picoseconds to several nanoseconds. The faster component could be correlated to inertial characteristics of the constituent ions, and the slower component to solvent viscosity. Dielectric continuum calculations of the sort previously used to predict solvation dynamics in dipolar liquids were shown to work poorly for predicting the response in these ionic liquids.

UR - http://www.scopus.com/inward/record.url?scp=34249650087&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34249650087&partnerID=8YFLogxK

U2 - 10.1021/jp067273m

DO - 10.1021/jp067273m

M3 - Article

C2 - 17319715

AN - SCOPUS:34249650087

VL - 111

SP - 4978

EP - 4989

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 18

ER -