PUB - Publikationen an der Universität Bielefeld

Abstract Frequency-swept pulses have recently been introduced as pump pulses into double electron-electron resonance (DEER) experiments. A limitation of this approach is that the pump pulses need to be short in comparison to dipolar evolution periods. The ”chirp-induced dipolar modulation enhancement” (CIDME) pulse sequence introduced in this work circumvents this limitation by means of longitudinal storage during the application of one single or two consecutive pump pulses. The resulting six-pulse sequence is closely related to the five-pulse ”relaxation-induced dipolar modulation enhancement” (RIDME) pulse sequence: While dipolar modulation in \{RIDME\} is due to stochastic spin flips during longitudinal storage, modulation in \{CIDME\} is due to the pump pulse during longitudinal storage. Experimentally, \{CIDME\} is examined for Gd-Gd and nitroxide-nitroxide distance determination using a high-power Q-band spectrometer. Since longitudinal storage results in a 50% signal loss, comparisons between \{DEER\} using short chirp pump pulses of 64 ns duration and \{CIDME\} using longer pump pulses are in favor of DEER. While the lower sensitivity restrains the applicability of \{CIDME\} for routine distance determination on high-power spectrometers, this result is not to be generalized to spectrometers having lower power and to specialized ”non-routine” applications or different types of spin labels. In particular, the advantage of prolonged \{CIDME\} pump pulses is demonstrated for experiments at large frequency offset between the pumped and observed spins. At a frequency separation of 1 GHz, a Gd-Gd modulation depth larger than 10% is achieved, where broadening due to dipolar pseudo-secular contributions becomes largely suppressed. Moreover, a \{CIDME\} experiment at deliberately reduced power underlines the potential of the new technique for spectrometers with lower power, as often encountered at higher microwave frequencies. With longitudinal storage times T below 10 μ s, however, \{CIDME\} appears rather susceptible to artifacts. For nitroxide-nitroxide experiments, these currently inhibit a faithful data analysis. To facilitate further developments, the artifacts are characterized experimentally. In addition, effects that are specific to the high spin of S = 7 / 2 Gd-centers are examined. Herein, population transfer within the observer spin’s multiplet due to the pump pulse as well as excitation of dipolar harmonics are discussed.