title: Fitting of deuterium quadrupole echo spectra with multiple motional models.
abstract: Dynamic information is generally extracted from deuterium quadrupole echo spectra by matching a spectrum calculated for a particular motional model to the experimental spectrum. In this work, a set of computer programs has been written to facilitate fitting of calculated spectra to experimental spectra that represent from one to five motional models. The fitting program requires pre-calculated libraries of spectra for the models of interest, and accomplishes the fitting either by a systematic method or by simulated annealing. The systematic method is convenient for fitting with one or two motional models, but the simulated annealing method is faster for two or more models, if the libraries are made up of hundreds of spectra. The parameter Q, with the standard deviation of the spectral points estimated as the standard deviation of the baseline noise, provides a stringent measure of goodness of fit. Acceptable fits of experimental data as judged by this criterion have not been found, even in the case of ring flip motion in phenylalanine-d(5) in which the fit may be judged acceptable by eye. An example of fitting with isotropic and methyl rotation motional models of alanine-d(3), which have distinct spectral patterns, shows that it is possible to obtain reasonably accurate estimates of the relative amounts of deuterium representing the different models, even from poorly fitted spectra.
authors.affiliation: Department of Chemistry, Oklahoma State University, Stillwater, OK 74078-0447, USA. meastman@chem.okstate.edu
authors.forename: Margaret A
authors.initials: MA
authors.lastname: Eastman
authors.forename: Mark A
authors.initials: MA
authors.lastname: Nanny
mesh_terms: D000465:Algorithms; D003198:Computer Simulation; D003903:Deuterium / Q000737:chemistry*; D017352:Echo-Planar Imaging / Q000379:methods*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008956:Models, Chemical
chemical_list: D003903:Deuterium