Electron spin resonance line widths of transition metal ions in solution. Relaxation through zero-field splitting

The factors which determine the electron resonance line widths of transition metal complexes in solution are considered. For complex ions possessing two or more unpaired electrons the dominant relaxation mechanism arises from coupling of the zero-field splitting of the spin multiplet with the random tumbling of the molecules in fluid solution. The theory of this effect is re-examined using the time-dependent density matrix methods of Redfield.