Nuclear spin relaxation in aqueous paramagnetic ion solutions
Abstract
An angular timedependent probability density function describing Brownian or anomalous rotational dynamics of fixedlength atomtoatom vectors is presented. The probability density function, which fully incorporates angular boundary conditions, is applied to aqueous ion complexes. The rotational dynamics of ion$^1$H vectors are shown by molecular dynamics (MD) simulation to be Brownian. A Brownian shell model is presented which yields a closed form expression for the frequencydependent nuclearmagneticresonance spinlattice relaxation rate $T_1^{1}(\omega)$ based on a distance parameter and time constant. Appropriate combinations of shell and/or continuum models are shown to provide excellent fullyquantitative fits to experimental $T_1^{1}(\omega)$ dispersion curves from aqueous manganese(II), iron(III) and copper(II) chloride solutions. The distance parameters and time constants obtained from the fits are in good agreement with independent experimental and MD data in the literature. The Brownian shell model is a significant enhancement to existing particleparticle models that describe the rotational correlation function as a single exponential and are unable to provide the correct distance dependence for a shell of $^1$H spin density preventing a match to experiment without an arbitrary scaling factor.
 Publication:

arXiv eprints
 Pub Date:
 September 2021
 arXiv:
 arXiv:2109.05610
 Bibcode:
 2021arXiv210905610F
 Keywords:

 Condensed Matter  Other Condensed Matter;
 Physics  Chemical Physics
 EPrint:
 39 pages, 7 figures, includes an appendix