The spectral forms of transient ESR spectra of radical pairs and the origin of the antiphase structure

Abstract

We show that transient electron spin resonance (ESR) spectra of short lived radical pairs can be written formally as a superposition of Lorentzian-like lines and the corresponding dispersive lines. The coefficients to these spectral components depend strongly on the frequency and amplitude of the microwave (mw) field and consequently a variety of spectral forms may result. The coefficients, and thus the spectral form, are determined by the interradical interaction induced rate of change of the longitudinal and transversal electron spin polarization. The longitudinal polarization is responsible for the well known chemically induced dynamic electron polarization (CIDEP) which changes the intensity of the lines without affecting the line shape. The transversal polarization is shown to be responsible for the antiphase structure (APS) in accordance with our previous proposition [J. Chem. Phys. 109, 8743 (1998)]. A simple one re-encounter model calculation illustrates and explains qualitatively most of the observed APS characteristics. Numerical calculations are used to discuss anomalously large APS splitting.