the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Floquet Theory and Average Hamiltonian Theory Revisited: Equivalence, Convergence and Applications to NMR
Abstract. An accurate theoretical treatment of periodically driven quantum systems is crucial for various fields in the exact sciences, for instance Nuclear Magnetic Resonance (NMR) spectroscopy. Conventionally, either average Hamiltonian theory or Floquet theory is used to predict or describe experimental outcomes, such as the time evolution or the spectra yielding the information of the sample under study. A detailed analysis of the equivalence of these two approaches with an emphasis on applications in NMR will help to improve the theoretical understanding of NMR experiments.
In this work, we identify the Floquet–Magnus expansion as essential to prove the mathematical equivalence of Floquet theory and average Hamiltonian theory. We advocate a calculation scheme which is less prone to algebraic mistakes because explicit integration is avoided. On this basis, we provide the first four orders of both theories. We further examine their applicability to some experiments in NMR. As examples, we investigate the Bloch–Siegert shift and dipolar coupled spin systems under magic-angle spinning.
Based on our analysis, we recommend the use of the Floquet–Van Vleck approach including both the effective Hamiltonian and the kick operator. The consistent separation of secular and non-secular contributions appears to be especially advantageous for numerical robustness. Its accuracy is about three times better than the one provided by average Hamiltonian theory despite their formal equivalence.
Our findings provide important insights into the theoretical background of Floquet theory and average Hamiltonian theory. This includes the extent of their algebraic and perturbative equivalence, with an emphasis on how these findings are of relevance in the analysis of solid-state NMR experiments.
Competing interests: Matthias Ernst, who is one of the (co-)authors, is a member of the editorial board of Magnetic Resonance.
Publisher's note: Copernicus Publications remains neutral with regard to jurisdictional claims made in the text, published maps, institutional affiliations, or any other geographical representation in this paper. While Copernicus Publications makes every effort to include appropriate place names, the final responsibility lies with the authors. Views expressed in the text are those of the authors and do not necessarily reflect the views of the publisher.- Preprint
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Status: open (until 09 Oct 2026)
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CC1: 'Comment on mr-2026-10', Tom Barbara, 24 Sep 2026
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CC2: 'Reply on CC1', Matthias Ernst, 24 Sep 2026
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Dear Tom,
thank you for the positive words about our manuscript.
We hope that the analytical equations up to fourth order are helpful in situations where such higher orders are needed.
I think the reason the Bloch-Siegert shift is often not noticed stems from the fact that all lines in the spectrum shift the same amount and we typically observe only relative frequencies. And if you always decouple, you have no reference to notice the shift. However, there have been recent publications where the heteronuclear Bloch-Siegert shift was observed and even utilized to calibrate the rf-field amplitude of low-γ nuclei (I. Hung, P. Gor’kov, Z. Gan, Using the heteronuclear Bloch-Siegert shift of protons for B1 calibration of insensitive nuclei not present in the sample, J. Magn. Reson. 310 (2020) 106636–5. https://doi.org/10.1016/j.jmr.2019.106636. and E. Nehra, V. Agarwal, Y. Nishiyama, Low-power 14N decoupling at fast MAS of 70 kHz, Solid State Nucl. Magn. Reson. 137 (2025) 102006. https://doi.org/10.1016/j.ssnmr.2025.102006.). The Bloch-Siegert shift is much stronger if you irradiate (decouple) the low-γ nucleus while observing the high-γ nucleus than the other way round. In this situation, even a field of 40 kHz nutation frequency on 14N can lead to a Bloch-Siegert shift of 500 Hz on the protons. When I was last sitting at the spectrometer myself and measuring 15N-1H correlation spectra, I actually noticed for the first time the significant shift of protons when decoupling 15N during the acquisition from undecoupled spectra.
I agree that Shirley's thesis is worthwhile reading. It has a lot more context than the Phys.Rev. article from 1965.
Best regards,
Matthias
Citation: https://doi.org/10.5194/mr-2026-10-CC2 -
CC3: 'Reply on CC2', Tom Barbara, 24 Sep 2026
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HI Matthias,
Thanks for mentioning those heteronuclear decoupling papers. This reminded me of how confusing things can get with the use of the terminology. Of course, once transverse magnetization is created by a resonant pulse, a very weak far off resonance irradiation can produce a phase or frequency shift. This method is used in MRI to map B1 fields and those researchers that pursue such matters always refer this as a "Bloch-Siegert" shift. I always found this aspect confusing because to me Bloch-Siegert was about the "counter rotating component", which has a very different symmetry under rotations. I can recall this confusion at the very start from the papers by Bodenhausen and Emsley. Not to long ago I became motivated to write up a short note about this because some coworkers were interested in mapping B1 of a head coil for out 7T whole body scanner and wanted to know how it worked. If you are interested, I have added my note as a supplement. The calculation appears to give the same result as Hung, Gorkov and Gan who mentioned in the introduction the "AC stark effect" and give the expression w1^2/2*(delta).
Thanks again for an interesting discussion and the references.
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CC3: 'Reply on CC2', Tom Barbara, 24 Sep 2026
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CC2: 'Reply on CC1', Matthias Ernst, 24 Sep 2026
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This is a very useful effort to have available, especially the comparison with Average Hamiltonian Theory. The calculation out to 3rd order for Bloch Siegert is very revealing. Since I worked on micro-coil NMR and had read about some groups that enjoyed 1 MHz Rabi frequencies, I often wondered why no one observed such shifts. On a historical note, this inspired me to look up J.H. Shirley's Cal Tech thesis, which I borrowed via inter library loan when I was a post doc at UCSD. Now of course, you can get it right away via the Cal Tech web site!