Nonlinear susceptibility of superparamagnets with a general anisotropy energy J. L. Garcı ´ a-Palacios,* P. Jo ¨ nsson, and P. Svedlindh Department of Materials Science, Uppsala University, Box 534, SE-751 21 Uppsala, Sweden Received 13 July 1999; revised manuscript received 5 October 1999 The equilibrium nonlinear response of noninteracting superparamagnets with a general single-spin anisot- ropy is investigated. Generalizing the results obtained for the simplest uniaxial anisotropy Garcı ´a-Palacios and La ´zaro, Phys. Rev. B 55, 1006 1997, we derive a formula for the nonlinear susceptibility of spin ensembles with randomly distributed anisotropy axes, ¯ (3) , valid for any magnetic anisotropy with inversion symmetry. The analysis of this expression reveals that: i ¯ (3) is always negative, iiunlike the linear susceptibility, ¯ (3) remains anisotropy dependent after the random axes average except for cubic anisotropy, for which ¯ (3) is equal to that of isotropic spins, iiithe anisotropy always increases the magnitude of the nonlinear response, and ivsince this increase depends on temperature, ¯ (3) deviates from the common ¯ (3) T -3 laws. The general expression for ¯ (3) is finally particularized to superparamagnets with competing uniaxial and cubic anisotropies and superparamagnets with biaxial anisotropy arbitrary ‘‘shape’’ anisotropy, for which we study the crossovers between the different regimes isotropic, discrete orientation, and plane rotatorinduced by the magnetic anisotropy. I. INTRODUCTION The study of classical spin systems has shed much light on the properties of their quantum counterparts and consti- tutes, in addition, an important field of research in its own right. Besides, there exist certain systems for which a de- scription in terms of classical spins captures the essential physics in certain ranges, for instance, molecular magnetic clusters with high spin in their ground state ( S 10) and magnetic nanoparticles ( S 10 2 –10 5 ); both systems will here be referred to as superparamagnets. Although we use the language of magnetism, we could also include here sys- tems as the so-called relaxor ferroelectrics, in which the net polarization of small polar regions can reorient due to ther- mal activation between several equienergetical orientations, leading to a superparaelectric behavior. Among the various experimental realizations of super- paramagnets, some approximately consist of noninteracting entities. The understanding of the properties of classical, noninteracting systems is besides very important for the sub- sequent study of their quantum, interacting counterparts. For example, owing to an insufficient knowledge about some properties of independent superparamagnets, it is not always known from which ‘‘laws’’ the associated quantities depart as a consequence of interspin interactions. Similar consider- ations also apply to the study of quantum phenomena in these systems; as complete a knowledge as possible of the classical regime is a prerequisite for the study of, for in- stance, quantum tunneling and coherence. A. Magnetic anisotropy and extent of the equilibrium superparamagneticrange The single-spin anisotropy plays a fundamental role in the behavior of superparamagnets. Nevertheless, the effects of the anisotropy on the thermal-equilibrium properties of these systems are sometimes overlooked because superparamag- netism is restrictively ascribed to the temperature range in which the heights of the energy barriers created by the mag- netic anisotropyare lower than the thermal energy. Let us briefly show the limitations of this view. In the moderate-to-high barrier range, the characteristic time for the rotation of a classical spin m over the energy barrier U can be written in the Arrhenius form = 0 exp U , 1.1 where =1/k B T and the pre-exponential term is weakly de- pendent on temperature ( 0 10 -7 –10 -8 s for molecular magnetic clusters and 0 10 -10 –10 -12 s for magnetic nanoparticles. Then, for a given measurement time t m , the spins display their thermal-equilibrium response when the condition of superparamagnetism, t m , is obeyed, which corresponds to the temperature range: lnt m / 0 U 0. 1.2 For instance, for ‘‘static’’ measurements ( t m 1 –100 s) this range is extremely wide (25U 0), showing that the mentioned ascription of superparamagnetism to the range in which the thermal energy is larger than the anisotropy barri- ers (1 U 0) is unduly restrictive. The preceding considerations also entail that, without leaving the superparamagnetic regime, there are ranges in which U 1 isotropic behavior, U 1 intermediate behavior, or U 1 discrete-orientation behavior. Thus, common approaches such as the isotropic or the discrete- orientation ones have a restricted range of validity for them- selves, while, even with the combined use of both, the effects of the crossover between the different ranges are lost. B. Linear and nonlinear responses One of the most informative tools to investigate the prop- erties of spin systems is the analysis of its linear response. This analysis could give, for instance, important information about the symmetry and strength of the magnetic anisotropy PHYSICAL REVIEW B 1 MARCH 2000-II VOLUME 61, NUMBER 10 PRB 61 0163-1829/2000/6110/67268/$15.00 6726 ©2000 The American Physical Society