Bloess A, Mobius K, Prisner TF
Freie Universitat Berlin, Arnimallee 14, Berlin, D-14195, Germany.
J Magn Reson. 1998 Sep;134(1):30-5. doi: 10.1006/jmre.1998.1474.
High-frequency/high-field (95 GHz/3.4 T) electron spin echo envelope modulation (ESEEM) experiments on single crystals and disordered samples of dianisyl-nitroxide (DANO) radicals are reported. At these high microwave frequencies (W-band), the anisotropic g-matrix of the nitroxide radical is resolved in the EPR spectrum. Additionally ESEEM modulations from other than nitrogen nuclei, such as protons, are highly suppressed at these frequencies, because they are too far from the cancellation condition for effective mixing of the nuclear spin functions. Therefore the nitrogen (14N) hyperfine and quadrupole coupling tensors could be determined without ambiguity from powder measurements. The results obtained were checked by ESEEM measurements on single crystals. Advantages and disadvantages of high-field ESEEM on nitrogen couplings are briefly discussed and compared with electron nuclear double resonance (ENDOR) and X-band ESEEM. Copyright 1998 Academic Press.
报道了对二茴香基氮氧化物(DANO)自由基的单晶和无序样品进行的高频/高场(95GHz/3.4T)电子自旋回波包络调制(ESEEM)实验。在这些高微波频率(W波段)下,氮氧化物自由基的各向异性g矩阵在电子顺磁共振(EPR)谱中得到分辨。此外,在这些频率下,来自氮核以外的其他核(如质子)的ESEEM调制受到高度抑制,因为它们距离核自旋函数有效混合的抵消条件太远。因此,通过粉末测量可以明确确定氮(14N)超精细和四极耦合张量。通过对单晶的ESEEM测量对所得结果进行了检验。简要讨论了高场ESEEM在氮耦合方面的优缺点,并与电子核双共振(ENDOR)和X波段ESEEM进行了比较。版权所有1998年学术出版社。