Relaxation theory of the electronic spin of a complexed paramagnetic metal ion in solution beyond the Redfield limit.

The relaxation of the electronic spin S of a paramagnetic metal ion with fully quenched orbital angular momentum in its ground state is investigated in an external magnetic field through a systematic study of the time correlation functions governing the evolution of the statistical operator (density matrix). Let omega0 be the Larmor angular frequency of S. When the relaxation is induced by a time-fluctuating perturbing Hamiltonian hH1(t) of time correlation tauc, it is demonstrated that after a transient period the standard Redfield approximation is relevant to calculate the evolution of the populations of the spin states if parallelH1 parallel2tauc2/(1+omega0(2)tauc2)<<1 and that this transient period becomes shorter than tauc at sufficiently high field for a zero-field splitting perturbing Hamiltonian. This property, proven analytically and confirmed by numerical simulation, explains the surprising success of several simple expressions of the longitudinal electronic relaxation rate 1/T1e derived from the Redfield approximation well beyond its expected validity range parallelH1 paralleltauc<<1. It has favorable practical consequences on the interpretation of the paramagnetic relaxation enhancement of nuclei used for structural and dynamic studies.