ESR-Linienbreite der Ionen der Eisengruppe in Lösungen
Electron spin resonance linewidths of ions belonging to the first transition group with quenched orbital angular momentum are calculated using a modified relaxationmatrix theory including third and fourth order perturbation terms. We base our calculation on a Hamiltonian, which depends on electron spin, nuclear spin, orbital angular momentum, rotation of the whole complex, and vibration of the ligands. Quadrupol effects, intermolecular electron-electron and electron-nucleus interactions are neglected. The results show that the well-known formula of the transverse relaxation time derived by using the spin-Hamiltonian is correct, if first the contribution of the rotational spin orbit process is taken in consideration and second the rotational correlation timeτc is replaced byτv=(1/τc+1/τ(0))−1. 1/τ(0) describes the linewidth of the lowest energy value of the electrostatic energy of unpaired electrons in the ligand field. The linewidth arises from the normal modes of the complex; the calculation gives τ(0)=l0−11...10−12 sec.