title: Simulating Frequency-Domain Electron Paramagnetic Resonance: Bridging the Gap between Experiment and Magnetic Parameters for High-Spin Transition-Metal Ion Complexes.
abstract: We present a comparison of experimental and simulated frequency- and field-domain electron paramagnetic resonance (EPR) spectra of integer and half-integer high-spin transition-metal ion complexes. For the simulation of EPR spectra a new tool within the EPR simulation software EasySpin is introduced, which allows for field- and frequency-domain EPR simulations with the same theoretical model and the same set of spin Hamiltonian parameters. The utility of this approach is demonstrated on the integer-spin complexes NiBr2(PPh3)2 and [Tp2Mn]SbF6 (both S = 1) and the half-integer-spin Fe(III) porphyrins, hemin (Fe(PPIX)Cl) and Fe(TPP)Cl (both S = 5/2). We demonstrate that the combination of field- and frequency-domain EPR techniques allows the determination of spin Hamiltonian parameters, in particular large zero-field splittings, with high accuracy.
authors.affiliation: Berlin Joint EPR Lab, Institute for Nanospectroscopy, Helmholtz-Zentrum Berlin für Materialien und Energie , Kekuléstraße 5, 12489 Berlin, Germany.
authors.forename: Joscha
authors.initials: J
authors.lastname: Nehrkorn
authors.affiliation: Department of Biological, Chemical and Physical Sciences, Roosevelt University , 430 South Michigan Avenue, Chicago, Illinois 60605, United States.
authors.forename: Joshua
authors.initials: J
authors.lastname: Telser
authors.affiliation: Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie , Albert-Einstein-Straße 15, 12489 Berlin, Germany.
authors.forename: Karsten
authors.initials: K
authors.lastname: Holldack
authors.affiliation: Department of Chemistry, University of Washington , Box 351700, Seattle, Washington 98195, United States.
authors.forename: Stefan
authors.initials: S
authors.lastname: Stoll
authors.affiliation: Berlin Joint EPR Lab, Institute for Nanospectroscopy, Helmholtz-Zentrum Berlin für Materialien und Energie , Kekuléstraße 5, 12489 Berlin, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Schnegg