Pulsed triple electron resonance (TRIER) for dipolar correlation spectroscopy.

Abstract

A new pulse sequence is presented for correlating dipolar frequencies in molecules with more than two paramagnetic centers. This triple electron resonance experiment (TRIER) is an extension the double electron-electron resonance (DEER) experiment, which is widely used for distance determination in the nanometer range. We use linear chirp pulses with smoothed edges to create a refocused observer echo, and two hyperbolic secant pulses with distinct excitation windows to excite two other subsets of spins. These pumped spins are coupled to the observed spin through the dipole-dipole interaction. A two-dimensional dipolar modulation pattern is recorded by variation of the position of the two pump pulses. By two-dimensional Fourier transform of the echo integral, a plot is obtained that correlates dipolar frequencies within the same molecule. Such correlation patterns can be used in conjunction with DEER, with which distance distributions are usually determined for several doubly labeled molecules with different spin-labeling sites. In the presence of two conformers, DEER traces give two distances and assignment to an individual conformer is not trivial and usually requires a trial and error approach. TRIER can potentially provide the missing connection between distances as correlations between dipolar frequencies.