Simulating suppression effects in pulsed ENDOR, and the 'hole in the middle' of Mims and Davies ENDOR spectra

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

doi:10.1007/s00723-009-0083-6

Simulating suppression effects in pulsed ENDOR, and the 'hole in the middle' of Mims and Davies ENDOR spectra

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

Chemistry

Research output: Contribution to journal › Article › peer-review

30 Scopus citations

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 = 1/2 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.

Original language	English (US)
Pages (from-to)	763-779
Number of pages	17
Journal	Applied Magnetic Resonance
Volume	37
Issue number	1
DOIs	https://doi.org/10.1007/s00723-009-0083-6
State	Published - 2010

Funding

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.

ASJC Scopus subject areas

Atomic and Molecular Physics, and Optics

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title = "Simulating suppression effects in pulsed ENDOR, and the 'hole in the middle' of Mims and Davies ENDOR spectra",

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 = 1/2 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.",

author = "Doan, {Peter E.} and Lees, {Nicholas S.} and Muralidharan Shanmugam and Hoffman, {Brian M.}",

note = "Funding Information: 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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doi = "10.1007/s00723-009-0083-6",

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AU - Doan, Peter E.

AU - Lees, Nicholas S.

AU - Shanmugam, Muralidharan

AU - Hoffman, Brian M.

N1 - Funding Information: 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.

PY - 2010

Y1 - 2010

N2 - 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 = 1/2 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.

AB - 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 = 1/2 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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Simulating suppression effects in pulsed ENDOR, and the 'hole in the middle' of Mims and Davies ENDOR spectra

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