10.
A theoretical approach to calculate the time evolution of magnetization during a CPMG pulse sequence of arbitrary parameter settings is developed and verified by experiment. The analysis reveals that off-resonance effects can cause systematic reductions in measured peak amplitudes that commonly lie in the range 5–25%, reaching 50% in unfavorable circumstances. These errors, which are finely dependent upon frequency offset and CPMG parameter settings, are subsequently transferred into erroneous
T2values obtained by curve fitting, where they are reduced or amplified depending upon the magnitude of the relaxation time. Subsequent transfer to Lipari–Szabo model analysis can produce significant errors in derived motional parameters, with τ
einternal correlation times being affected somewhat more than
S2order parameters. A hazard of this off-resonance phenomenon is its oscillatory nature, so that strongly affected and unaffected signals can be found at various frequencies within a CPMG spectrum. Methods for the reduction of the systematic error are discussed. Relaxation studies on biomolecules, especially at high field strengths, should take account of potential off-resonance contributions.
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