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  4. Ultrafast solvent response upon a change of the solute size in non-polar supercritical fluids
 
research article

Ultrafast solvent response upon a change of the solute size in non-polar supercritical fluids

Larrégaray, P.
•
Cavina, A.  
•
Chergui, M.  
2005
Chemical Physics

Non-polar solvation dynamics has been investigated using steady-state absorption and emission spectroscopy of the NO A(2)Sigma(+)(3ssigma) Rydberg state in fluid Ar over a wide range of densities spanning the supercritical regime. Equilibrium molecular dynamics simulations were implemented to derive a new isotropic NO A(3ssigma)-Ar pair potential which was further used to investigate the role of local density enhancements on the solvation process by non-equilibrium molecular dynamics simulations. These density inhomogeneities were found to have no influence on the solvation dynamics. Furthermore, the latter was shown to take place in a strongly non-linear regime, especially at low temperatures. This process results from the dramatic change of solute-solvent short range interaction associated with the large solute size change upon excitation to the Rydberg state.

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Type
research article
DOI
10.1016/j.chemphys.2004.07.047
Web of Science ID

WOS:000225814200003

Author(s)
Larrégaray, P.
Cavina, A.  
Chergui, M.  
Date Issued

2005

Published in
Chemical Physics
Volume

308

Issue

1-2

Start page

13

End page

25

Subjects

POLAR SOLVATION DYNAMICS

•

VISCOELASTIC CONTINUUM MODEL

•

LENNARD-JONES FLUIDS

•

SHORT-TIME DYNAMICS

•

RARE-GAS MATRICES

•

CRITICAL-POINT

•

MOLECULAR THEORY

•

DENSITY INHOMOGENEITIES

•

VIBRATIONAL-RELAXATION

•

NONDIPOLAR SOLVENTS

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LSU  
Available on Infoscience
April 12, 2011
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/66339
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