2017/03/06 by Arnab Chakrabarti, Chakrabarti, Arnab, Rangeet Bhattacharyya +1
Chemistry · Physics and Astronomy · #Advanced NMR Techniques and Applications #FOS: Physical sciences #NMR spectroscopy and applications #Quantum Physics (quant-ph) #Spectroscopy and Quantum Chemical Studies #Statistical Mechanics (cond-mat.stat-mech)
paper · pdf · doi:10.48550/arxiv.1703.01954
openalex publication_date 2017/03/06 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
We report that the Bloch-Siegert shift which appears in Nuclear Magnetic Resonance (NMR) spectroscopy can also be shown to originate as a part of a complex drive-induced second-order susceptibility term. The shift terms thus obtained are shown to have an absorptive Kramers-Kronig pair. The theoretical treatment involves a finite time-propagation of a nuclear spin-1/2 system and the spin-bearing molecule under the action of thermal fluctuations acting on the latter. The finite propagator is constructed to account for many instances of thermal fluctuations occurring in a time-scale during which the spin density matrix changes infinitesimally. Following an ensemble average, the resulting quantum master equation directly yields a finite time-nonlocal complex susceptibility term from the external drive, which is extremely small but measurable in solution-state NMR spectroscopy. The dispersive part of this susceptibility term originating from the non-resonant component of the external drive results in the Bloch-Siegert shift. We have verified experimentally the existence of the absorptive Kramers-Kronig pair of the second-order shift term, by using a novel refocussed nutation experiment. Our method provides a single approach to explain both relaxation phenomena as well as Bloch-Siegert effect, which have been treated using non-concurrent techniques in the past.