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Simulating Suppression Effects in Pulsed ENDOR, and the ‘Hole in the Middle’ of Mims and Davies ENDOR Spectra

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Abstract

All pulsed electron-nuclear double resonance (ENDOR) techniques, and in particular the Mims and Davies sequences, suffer from detectability biases (‘blindspots’) that are directly correlated to the size of the hyperfine interactions of coupled nuclei. Our efforts at ENDOR ‘crystallography’ and ‘mechanism determination’ with these techniques have led our group to refine our simulations of pulsed ENDOR spectra to take into account these biases, and we here describe the process and illustrate it with several examples. We first focus on an issue whose major significance is not widely appreciated, the ‘hole in the middle’ of pulsed ENDOR spectra caused by the n = 0 suppression hole in Mims ENDOR and by the analogous A → 0 suppression in Davies ENDOR for I = ½ and for 2H (I = 1). We then discuss the general treatment of suppression effects for I = 1, illustrating it with a treatment of Mims suppression for 14N.

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Acknowledgments

We thank Prof. Michael J. Clarke (Boston College) for the preparation of trans-[(Imidazole)2(NH3)4Ru(III)]Cl3. This work has been supported by the National Institute of Health (HL 13531, B.M.H.) and National Science Foundation (MCB0723330, B.M.H.). It has benefitted from the superb technical support of Mr. Clark Davoust.

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  1. Department of Chemistry, Northwestern University, Evanston, IL, 60208-3113, USA

    Peter E. Doan, Nicholas S. Lees, Muralidharan Shanmugam & Brian M. Hoffman

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  1. Peter E. Doan
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  2. Nicholas S. Lees
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  3. Muralidharan Shanmugam
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  4. Brian M. Hoffman
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Correspondence to Brian M. Hoffman.

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Doan, P.E., Lees, N.S., Shanmugam, M. et al. Simulating Suppression Effects in Pulsed ENDOR, and the ‘Hole in the Middle’ of Mims and Davies ENDOR Spectra. Appl Magn Reson 37, 763–779 (2010). https://doi.org/10.1007/s00723-009-0083-6

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  • DOI: https://doi.org/10.1007/s00723-009-0083-6

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