Ea. Hill et Jp. Yesinowski, SOLID-STATE N-14 NUCLEAR-MAGNETIC-RESONANCE TECHNIQUES FOR STUDYING SLOW MOLECULAR MOTIONS, The Journal of chemical physics, 107(2), 1997, pp. 346-354
A variety of transition-selective solid-state N-14 (1 = 1)NMR techniqu
es are demonstrated for the first time to be useful for quantitatively
describing;slow molecular motions in the solid state. These technique
s are validated by quantitative measurements of molecular reorientatio
n by tetrahedral jumps in hexamethylenetetramine (HMT). A new four-sit
e magnetization-exchange model, capable of being generalized to n-site
s, which includes the effects of spin-lattice relaxation is developed.
This model provides the limiting conditions under which the orientati
on dependence of spin-lattice relaxation values T-1 can be safely negl
ected. The model is used to analyze results from a frequency-selective
DANTE train used to burn a hole in the spectrum, that provide a direc
t indication of the existence of 4-site exchange. The measured correla
tion time for the motion in HMT of 103+/-6 ms at room temperature agre
es well with previous studies by other techniques. In a novel applicat
ion to molecular dynamics, the repeated hole-burning pulse trains of t
he SINK experiment are used to measure a magnetization recovery time c
onstant due to N-14 spin-lattice relaxation in HMT of 0.99 +/- 0.12 s.
Both experiments employ frequency-selective as well as transition-sel
ective radio frequency pulses on a relatively small frequency region (
<100 kHz) of the entire quadrupolar powder pattern of HMT (NQCC=4.414
MHz, eta=0). The Hahn spin-echo used for detection can be understood i
n terms of the fictitious spin-1/2 formalism. Quantitative dynamical i
nformation is obtained from measurements at only one frequency positio
n of a wide inhomogeneously broadened powder pattern. Because we are o
perating in this unusual regime, the sensitivity can be significantly
improved by replacing the DANTE hole-burning train with a series of pi
/2 pulses that saturate all observable magnetization. Results from suc
h an experiment compare well with those obtained using DANTE trains. (
C) 1997 American Institute of Physics.