V. VARIOUS OPERATOR FORMALISMS FOR THE
DESCRIPTION OF PULSE METHODS IN NMR
Geoffrey BODENHAUSEN
Institut de Chimie Organique
Universite de Lausanne
Rue de Ia Barre 2
CH-1005 Lausanne
Switzerland
ABSTRACT. A brief survey of various operator formalisms is presented in order to provide some
clues as to which type of theory is most suitable for the description of various experiments.
1. Introduction
In recent years, much attention has been given to various operator formalisms designed to
simplify the description of more or less sophisticated pulse experiments. It is often difficult
to assess which formalism (if any) is needed to describe a given experimental situation. We
have to consider the nature of the spin system as well as the type of experiment. In this
context, spin systems differ in that they may be in isotropic or anisotropic phase, that they
mayor may not have resolved couplings, possess magnetically equivalent subsets, etc.
Experimental techniques differ in that they may merely employ pulses with flip angles of
90
0
and multiples thereof, or use arbitrary flip angles; in that they may include pulse
sandwiches designed to induce composite rotations; in that they may incorporate the
selection of coherence pathways by phase-cycling, etc.
Apart from the well-known papers by S(.!Irensen et al.(l), van der Yen and Hilbers (2),
and by Wright and Packer (3), the subject is extensively reviewed in Ernst's monograph
(4). A lucid recapitulation, entitled "density-operator theory of pulses and precession", was
written by Levitt some years ago and published only recently (5). Some recent extensions
using products of tensor operators to describe equivalent protons in methyl groups have
been published by Muller et al. (6), while Jaccard et al. (7) have applied similar concepts to
S = 3/2 spins. The description of strongly coupled systems with the help of operator
products (rather than the usual density matrix representations) has been addressed very
recently by Kay and McClung (8). A useful compilation of matrix representations of
operator products is contained in the appendix of Chandrakumar and Subramanian's book
(9), who also give many non-trivial examples of operator treatments. The volume by
Gerstein and Dybowski (to) also contains many enlightening chapters on operators.
51
P. Granger and R. K. Harris (eds.)
Multinuclear Magnetic Resonance in Liquids and Solids - Chemical Applications, 51-61.
© 1990 Kluwer Academic Publishers.