Fischer Jörg Wolfgang Anselm, Stropp Julian, Tschaggelar René, Oberhänsli Oliver, Alaniva Nicholas, Inoue Mariko, Mashima Kazushi, Barnes Alexander Benjamin, Jeschke Gunnar, Klose Daniel
Institute for Molecular Physical Science, ETH Zurich, Vladimir-Prelog-Weg 2, 8093 Zurich, Switzerland.
Department of Chemistry Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama-cho, Toyonaka, Osaka 560-8531, Japan.
Magn Reson (Gott). 2024 Sep 20;5(2):143-152. doi: 10.5194/mr-5-143-2024. eCollection 2024.
Continuous-wave electron paramagnetic resonance (EPR) spectroscopy at 35 GHz is an essential cornerstone in multi-frequency EPR studies and is crucial for differentiating multiple species in complex systems due to the improved -tensor resolution compared to lower microwave frequencies. Especially for unstable and highly sensitive paramagnetic centers, the reliability of the measurements can be improved upon through the use of a single sample for EPR experiments at all frequencies. Besides the advantages, the lack of common availability of oversized-sample resonators at 35 GHz often limits scientists to lower frequencies or smaller sample geometries, and the latter may be non-trivial for sensitive materials. In this work, we present the design and performance of an oversized-sample 35 GHz EPR resonator with a high loaded value, , of up to 2550, well-suited for continuous-wave EPR and pulsed single-microwave-frequency experiments. The design is driven by electromagnetic field simulations, and the microwave characteristics of manufactured prototypes were found to be in agreement with the predictions. The resonator is based on a cylindrical cavity with a TE mode, allowing for 3 mm sample access. The design targets that we met include high sensitivity, robustness, and ease of manufacturing and maintenance. The resonator is compatible with commercial EPR spectrometers and with helium flow, as well as with cryogen-free cryostats, allowing for measurements at temperatures down to 1.8 K. To highlight the general applicability, the resonator was tested on metal centers, as well as on organic radicals featuring extremely narrow lines.
35GHz连续波电子顺磁共振(EPR)光谱学是多频EPR研究的重要基石,由于与较低微波频率相比,其张量分辨率有所提高,因此对于区分复杂系统中的多种物质至关重要。特别是对于不稳定且高度敏感的顺磁中心,通过在所有频率下使用单个样品进行EPR实验,可以提高测量的可靠性。除了这些优点外,35GHz超大样品谐振器的普遍缺乏常常限制科学家只能使用较低频率或较小的样品几何尺寸,而对于敏感材料来说,后者可能并非易事。在这项工作中,我们展示了一种具有高达2550的高负载值的超大样品35GHz EPR谐振器的设计和性能,该谐振器非常适合连续波EPR和脉冲单微波频率实验。该设计由电磁场模拟驱动,并且发现制造的原型的微波特性与预测结果一致。该谐振器基于具有TE模式的圆柱形腔体,允许3mm的样品进入。我们实现的设计目标包括高灵敏度、鲁棒性以及易于制造和维护。该谐振器与商业EPR光谱仪兼容,与氦气流兼容,也与无液氦低温恒温器兼容,能够在低至1.8K的温度下进行测量。为了突出其普遍适用性,该谐振器在金属中心以及具有极窄谱线的有机自由基上进行了测试。