Tb. Woolf et al., THE BACKBONE N-15 CHEMICAL-SHIFT TENSOR OF THE GRAMICIDIN CHANNEL - AMOLECULAR-DYNAMICS AND DENSITY-FUNCTIONAL STUDY, Chemical physics letters, 239(1-3), 1995, pp. 186-194
The short-time-scale fluctuations in N-15 chemical shift tensors are e
xamined for an ensemble of N-methylacetamide complexes constructed fro
m a molecular dynamics (MD) trajectory of the gramicidin A channel in
a fully hydrated phospholipid bilayer. Sum-over-states density functio
nal perturbation theory (SOS-DFPT) calculations reveal fluctuations in
the magnitudes and orientations of the individual tenser components o
n the picosecond to femtosecond time scale. The MD/SOS-DFPT technique
emerges as a valuable tool for gaining insight into the nature of the
terms that enter the motionally averaged spectra observed experimental
ly. More extensive sampling should provide first-principles prediction
s of the spectra under experimental conditions.