Light-induced dipolar spectroscopy - A quantitative comparison between LiDEER and LaserIMD

TL;DR

This study compares two light-induced dipolar spectroscopy techniques, LiDEER and LaserIMD, for nanometric distance measurements using triplet porphyrin labels, highlighting improvements and performance differences at Q band.

Contribution

It provides a quantitative comparison of LiDEER and LaserIMD under equivalent conditions and demonstrates how chirp inversion pulses enhance LiDEER performance.

Findings

Chirp LiDEER significantly improves modulation depth.

LaserIMD outperforms LiDEER at short dipolar evolution times.

LiDEER's performance benefits from broadband pump pulses.

Abstract

Nanometric distance measurements with EPR spectroscopy yield crucial information on the structure and interactions of macromolecules in complex systems. The range of suitable spin labels for such measurements was recently expanded with a new class of light-inducible labels: the triplet state of porphyrins. Importantly, accurate distance measurements between a triplet label and a nitroxide have been reported with two distinct light-induced spectroscopy techniques, (light-induced) triplet-nitroxide DEER (LiDEER) and laser-induced magnetic dipole spectroscopy (LaserIMD). In this work, we set out to quantitatively compare the two techniques under equivalent conditions at Q band. Since we find that LiDEER using a rectangular pump pulse does not reach the high modulation depth that can be achieved with LaserIMD, we further explore the possibility of improving the LiDEER experiment with chirp inversion pulses. LiDEER employing a broadband pump pulse results in a drastic improvement of the modulation depth. The relative performance of chirp LiDEER and Laser-IMD in terms of modulation-to-noise ratio is found to depend on the dipolar evolution time: While LaserIMD yields higher modulation-to-noise ratios than LiDEER at short dipolar evolution times ({\tau}=2 {\mu}s), the high phase memory time of the triplet spins causes the situation to revert at {\tau}=6 {\mu}s.