title: Linewidth analysis of spin labels in liquids. I. Theory and data analysis.
abstract: We present a method of simulating the EPR spectra of spin labels in liquids using direct convolution of hyperfine splitting with Lorentzian linewidths. The aim is to simulate the experimental lineshape by considering all spectrometer characteristics as well as inhomogeneous and homogeneous linewidth effects. A major advance in this method is the correction for the broadening produced by Zeeman modulation commonly used to obtain EPR signals; this allows experimenters much more freedom to optimize their experimental conditions for the best signal-to-noise ratio. Microwave power broadening (saturation) effects on the EPR lines are significant even at very low observer levels. Successful simulation requires that all contributions from unresolved hyperfine splittings be explicitly included. Inhomogeneous broadening is dealt with by including all spins that interact with the electron (as a set of superhyperfine interactions); there is no "effective Gaussian" to substitute for the correct superhyperfine interactions. The effects of spin exchange on the linewidth and lineshape can be observed and must be taken into account in order to extract the fundamental linewidths.
authors.affiliation: Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.
authors.forename: B H
authors.initials: BH
authors.lastname: Robinson
authors.forename: C
authors.initials: C
authors.lastname: Mailer
authors.forename: A W
authors.initials: AW
authors.lastname: Reese
mesh_terms: D003198:Computer Simulation; D003497:Cyclic N-Oxides; D003627:Data Interpretation, Statistical; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods*; D008433:Mathematics; D008872:Microwaves; D008962:Models, Theoretical; D012680:Sensitivity and Specificity; D012984:Software; D013113:Spin Labels
chemical_list: D003497:Cyclic N-Oxides; D013113:Spin Labels; C047253:3-carbamoyl-2,2,5,5-tetramethyl-3-pyrroline-1-yloxyl