The role of stereoelectronic, environmental, and short-time dynamic effects in tuning the hyperfine and gyromagnetic tensors of a prototypical nitroxide spin probe was studied by an integrated computational approach based on extended Lagrangian mol. dynamics and discrete-continuum solvent models. Trajectories were generated in two protic solvents as well as in the gas phase for ref.; structural anal. of the dynamics, and comparison with optimized solute-solvent clusters, allowed for the identification of the prevailing solute-solvent hydrogen-bonding patterns and helped to define the strategy for the computation of magnetic parameters. This was performed in a sep. step, on a large no. of frames, by a high-level DFT approach coupling the PBE0 hybrid functional with a tailored basis set and with proper account of specific and bulk solvent effects. Remarkable changes in solvation networks are found on going from aq. to methanol soln., thus providing a rationalization of indirect exptl. available evidence. The computed magnetic parameters are in satisfactory agreement with the available measured values and allow for an unbiased evaluation of the role of different effects in tuning the overall EPR observables. Apart from their intrinsic interest, the authors' results pave the route toward the development of tunable detection protocols based on specific spectroscopic signatures.
Interplay of Intrinsic, Environmental, and Dynamic Effects in Tuning the EPR Parameters of Nitroxides: Further Insights from an Integrated Computational Approach / Pavone, Michele; P., Cimino; Crescenzi, Orlando; A., Sillanpaeae; Barone, Vincenzo. - In: JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL. - ISSN 1520-6106. - STAMPA. - 111:30(2007), pp. 8928-8939. [10.1021/jp0727805]
Interplay of Intrinsic, Environmental, and Dynamic Effects in Tuning the EPR Parameters of Nitroxides: Further Insights from an Integrated Computational Approach
PAVONE, MICHELE;CRESCENZI, ORLANDO;BARONE, VINCENZO
2007
Abstract
The role of stereoelectronic, environmental, and short-time dynamic effects in tuning the hyperfine and gyromagnetic tensors of a prototypical nitroxide spin probe was studied by an integrated computational approach based on extended Lagrangian mol. dynamics and discrete-continuum solvent models. Trajectories were generated in two protic solvents as well as in the gas phase for ref.; structural anal. of the dynamics, and comparison with optimized solute-solvent clusters, allowed for the identification of the prevailing solute-solvent hydrogen-bonding patterns and helped to define the strategy for the computation of magnetic parameters. This was performed in a sep. step, on a large no. of frames, by a high-level DFT approach coupling the PBE0 hybrid functional with a tailored basis set and with proper account of specific and bulk solvent effects. Remarkable changes in solvation networks are found on going from aq. to methanol soln., thus providing a rationalization of indirect exptl. available evidence. The computed magnetic parameters are in satisfactory agreement with the available measured values and allow for an unbiased evaluation of the role of different effects in tuning the overall EPR observables. Apart from their intrinsic interest, the authors' results pave the route toward the development of tunable detection protocols based on specific spectroscopic signatures.File | Dimensione | Formato | |
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