Journal of Chemical Physics, Vol.113, No.8, 3289-3301, 2000
The study of the influence of Jahn-Teller coupling and low symmetry strain on the anomalous electron paramagnetic resonance spectrum of titanium(III) doped CsAl(SO4)(2)center dot 12H(2)O
The controversial EPR spectrum of titanium(III) as an impurity in cesium aluminum sulphate alum has been re-examined using conventional CW- and a novel pulsed-EPR technique, which monitors the nutation frequency as a function of field. The CW-spectra display a high degree of structure, which is interpreted as arising from chemically distinct titanium(III) species. The two-dimensional nutation spectrum maps the g(parallel to) vs g(perpendicular to) relation from just one crystal orientation, and to far greater precision than available from CW-EPR. This novel technique shows that the origin of the linewidths observed for some of the EPR lines is inhomogeneous broadening, the nature of which can be described adequately only in the two-dimensional nutation spectrum. Calculations of g(parallel to) vs g(perpendicular to) have been undertaken by numerical diagonalization of the vibronic Hamiltonian. It is found that the relationship between g(parallel to) and g(perpendicular to) can be modeled only by assuming that the titanium(III) ions are subject to both dynamic Jahn-Teller coupling and low symmetry strain. Furthermore, it is shown that the calculated g(parallel to) vs g(perpendicular to) relation is strongly dependent upon the nature of the vibronic interaction assumed. An excellent reproduction of the experimental data is obtained, using parameters consistent with those employed to model the susceptibility data of the isostructural cesium titanium sulphate alum.