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SOLVATION STRUCTURE AND DYNAMICS OF THE FE2+-FE3+ ION-PAIR IN WATER

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Title SOLVATION STRUCTURE AND DYNAMICS OF THE FE2+-FE3+ ION-PAIR IN WATER
 
Creator KUMAR, PV
TEMBE, BL
 
Subject time-dependent fluorescence
electron-transfer reactions
molecular-dynamics
polar-solvent
nonequilibrium solvation
dielectric-relaxation
polarization relaxation
computer-simulations
aqueous-solutions
charge-transfer
 
Description Computer simulations are performed to study the structure of the coordination shells of Fe+2 and Fe+3 ions fixed at a very close reactive separation. The simulations show that it is possible for the two octahedral aquo complexes, i.e., Fe(H2O)6(2+) and Fe(H2O)6(3+), to come as close as 5 angstrom without disrupting their coordination shells. The reorientational dynamics within the hydration shells of these ions at this separation is examined by studying the time correlation functions (TCFs) of the unit vectors on the water molecules and along the iron-oxygen vector. The quantities related to the solvent polarization relaxation during a change in the charge, the dipole moment, and the quadrupole moment located at the solute ions are examined by studying the corresponding TCFs in the system. The TCFs exhibited a bimodal response, with a very fast initial relaxation due to inertial motions of the solvent, followed by a long tail corresponding to a diffusive component. The polarization fluctuations are also estimated via the cavity field time correlation function (CFTCF), which is useful in the theory of electron transfer processes. The memory kernel or the time dependent friction (TDF) of the solvent is also estimated from the force-force time correlation function. The cross correlations between the Coulombic and the non-Coulombic components of the forces at the ions contribute significantly to the TDF.
 
Publisher AMER INST PHYSICS
 
Date 2011-07-16T14:47:17Z
2011-12-26T12:49:50Z
2011-12-27T05:35:34Z
2011-07-16T14:47:17Z
2011-12-26T12:49:50Z
2011-12-27T05:35:34Z
1992
 
Type Article
 
Identifier JOURNAL OF CHEMICAL PHYSICS, 97(6), 4356-4367
0021-9606
http://dx.doi.org/10.1063/1.463905
http://dspace.library.iitb.ac.in/xmlui/handle/10054/4456
http://hdl.handle.net/10054/4456
 
Language en