Hyperfine Decoupling of ESR Spectra Using Wavelet Transform

The objective of spectral analysis is to resolve and extract relevant features from experimental data in an optimal fashion. In continuous-wave (cw) electron spin resonance (ESR) spectroscopy, both [Formula: see text] values of a paramagnetic center and hyperfine splitting [Formula: see text] caused by its interaction with neighboring magnetic nuclei in a molecule provide important structural and electronic information. However, in the presence of [Formula: see text] - and/or [Formula: see text]-anisotropy and/or large number of resonance lines, spectral analysis becomes highly challenging. Either high-resolution experimental techniques are employed to resolve the spectra in those cases or a range of suitable ESR frequencies are used in combination with simulations to identify the corresponding [Formula: see text] and [Formula: see text] values. In this work, we present a wavelet transform technique in resolving both simulated and experimental cW-ESR spectra by separating the hyperfine and super-hyperfine components. We exploit the multiresolution property of wavelet transforms that allow the separation of distinct features of a spectrum based on simultaneous analysis of spectrum and its varying frequency. We retain the wavelet components that stored the hyperfine and/or super-hyperfine features, while eliminating the wavelet components representing the remaining spectrum. We tested the method on simulated cases of metal-ligand adducts at L-, S-, and X-band frequencies, and showed that extracted [Formula: see text] values, hyperfine and super-hyperfine coupling constants from simulated spectra, were in excellent agreement with the values of those parameters used in the simulations. For the experimental case of a copper(II) complex with distorted octahedral geometry, the method was able to extract [Formula: see text] and hyperfine coupling constant values, and revealed features that were buried in the overlapped spectra.