Relaxation-Time Determination from Continuous-Microwave Saturation of EPR Spectra

Abstract

Based on the theories of Portis and of Castner 50 years ago, different continuous-wave measurement procedures for analyzing the microwave saturation power dependence of inhomogeneously broadened EPR lines were developed. Although these procedures have been refined, they still use only a few selected points on the saturation curve. A non-linear least-squares procedure for analyzing the microwave-power dependence of inhomogeneously broadened lines using all data points on a saturation curve has been developed. This procedure provides a simple alternative method to obtain magnetic relaxation data when the more direct pulse-saturation techniques are not available or are less suitable. The latter includes applications of quantitative EPR such as dosimetry. Then microwave saturation data should be obtained under conditions similar to those used in the quantitative measurements, which are usually made on first derivative spectra recorded using continuous-wave spectrometers. Selected applications to benchmark literature data and within the field of EPR dosimetry are discussed. The results obtained illustrate that relaxation times comparable to those yielded by various pulse-saturation EPR techniques can be obtained. It appears as a systematic feature that, whenever the pulse EPR data are fitted using bi-exponential functions, the shortest relaxation times obtained are those that correspond best to those measured using the current continuous-wave saturation method.

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Tuning the effective spin-orbit coupling in molecular semiconductors

“…As a consequence, passage effects can distort the signal shape if the spin packets cannot relax between modulation cycles. This was avoided by choosing a sufficiently small modulation amplitude B m or frequency ω m so that ω m B m <<1/( γ e T 1 T 2 ) and the spin system remains continually in thermal equilibrium30.…”

Analysis of Relaxation Behavior of Free Radicals in Irradiated Cellulose Using Pulse and Continuous-Wave Electron Spin Resonance

“…These observations suggest that the carbon-centered radical is responsible for the overlapping of peaks and affects the relaxation times, T1 and T2. The relaxation times were also calculated theoretically using the CW-ESR parameter (Lund, 2009). We revealed that T1 and T2 from pulsed-ESR and CW-ESR were changed similarly before and after irradiation.…”

“…To determine T1 and T2, we used Lund's program (Lund, 2009). For a Gaussian envelope of Lorentzian spin packets, previous treatments have shown the EPR line shape can be expressed as…”