Journal of Chemical Physics, Vol.114, No.1, 409-415, 2001
Time-reversal of the evolution of a dipole-coupled, many-spin system under continuous resonant irradiation
Time-reversal of the evolution of a dipole-coupled, many-spin system under continuous resonant excitation with a radio-frequency (rf) field of arbitrary amplitude is demonstrated in solid-state H-1 nuclear magnetic resonance (NMR) experiments on polycrystalline adamantane. Time-reversed evolution is accomplished with an rf pulse sequence that generates an effective nuclear spin Hamiltonian that includes both dipole-dipole coupling and rf interaction terms, with signs opposite to those in forward evolution. The amplitude of the effective continuous rf field is varied by varying the phases of rf pulses in the sequence. Experiments show echo-like NMR signals under time-reversed evolution after forward evolution to an apparent quasieguilibrium state under continuous rf excitation. Such echolike signals are inconsistent with the hypothesis of spin temperature in the rotating frame, according to which the approach to quasiequilibrium under continuous rf excitation is an irreversible process. The use of this time-reversed evolution in multiple quantum (MQ) NMR spectroscopy is also demonstrated. MQ NMR spectra obtained with increasing excitation times exhibit a partial confinement of nuclear spin order to zero- and one-quantum operators. This novel behavior is shown to be a consequence of energy conservation.