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Influence of Solute-Solvent Hydrogen Bonding on Intramolecular Magnetic Exchange Interaction in Aminoxyl Diradicals: A QM/MM Broken-Symmetry DFT Study

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Title Influence of Solute-Solvent Hydrogen Bonding on Intramolecular Magnetic Exchange Interaction in Aminoxyl Diradicals: A QM/MM Broken-Symmetry DFT Study
 
Creator ALI, ME
OPPENEER, PM
DATTA, SN
 
Subject density-functional theory
nitrophenyl nitronyl nitroxide
transition-metal-complexes
correlation-energy
coupling-constants
water
approximation
polyradicals
oniom
 
Description We have investigated the effect of nitroxide radical-water hydrogen bonding (NO(center dot)center dot center dot center dot H(2)O) on the intramolecular magnetic exchange interaction (J) for biologically relevant aminoxyl diradicals. We adopt a combination of broken-symmetry density functional theory and the quantum mechanics/molecular mechanics (QM/MM) approach. We find that the presence of hydrogen bonding reorients the radical spin density on -NO(center dot). This phenomenon reduces the effective distance between the two interacting localized spin centers that eventually increases the intramolecular magnetic exchange interaction. We have also investigated the functional variation of the magnetic exchange interaction, using various GGA (BLYP, PBE, HCTH407), meta-GGA (TPSS, VXSC), and hybrid (O3LYP, B3LYP, B3P86, B3PW91, and PBE0) functionals.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-14T08:01:25Z
2011-12-26T12:48:16Z
2011-12-27T05:47:52Z
2011-07-14T08:01:25Z
2011-12-26T12:48:16Z
2011-12-27T05:47:52Z
2009
 
Type Article
 
Identifier JOURNAL OF PHYSICAL CHEMISTRY B, 113(16), 5545-5548
1520-6106
http://dx.doi.org/10.1021/jp901922j
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3903
http://hdl.handle.net/10054/3903
 
Language en