# Feedback Effect on Landau-Zener-Stückelberg Transitions in Magnetic Systems

## Abstract

We examine the effect of the dynamics of the internal magnetic field on the staircase magnetization curves observed in large-spin molecular magnets. We show that the size of the magnetization steps depends sensitively on the intermolecular interactions, even if these are very small compared to the intra-molecular couplings.

Magnetization dynamics of nanoscale magnets, i.e. systems like Mn<sub>12</sub>-acetate and Fe<sub>8</sub> have been studied experimentally and theoretically lately . At sufficiently low temperatures quantum effects are observed, due to the discreteness of the energy levels involved. When the magnetization of a crystal of such molecules is measured during a sweep of the external magnetic field, a staircase hysteresis loop is obtained. The steep parts of the staircase correspond to the values of the external magnetic field where there is a crossing of adiabatic energy levels. Several aspects of this quantum effect were studied in . In a zero-temperature calculation, one finds that the magnetization can only change in steps, very similar to the steps observed in recent experiments on high-spin molecules Mn<sub>12</sub>-acetate and Fe<sub>8</sub>. At every crossing, only two levels play a role and the transition probability can be calculated using the Landau-Zener-Stückelberg (LZS) mechanism . Two parameters determine the LZS transition: The energy splitting at the crossing and the sweep rate of the magnetic field.

The size of the energy splitting which leads to a LZS transition probability is determined by the off-diagonal terms in the Hamiltonian describing the system. A straightforward perturbative calculation shows that this splitting is roughly scales like $`\mathrm{\Gamma }^{2|\mathrm{\Delta }m|}`$ where $`\mathrm{\Gamma }`$ determines the magnitude of the off-diagonal terms and $`\mathrm{\Delta }m`$ denotes the difference in magnetisation of the two relevant levels. In the absence of a transverse applied field the energy-level splittings in the high-spin molecules mentioned above are so small that the probability for a single LZS transition is effectively zero, unless the applied longitudinal field is rather large (see for example ).

In the crystal the magnetic field felt by a particular molecule is the sum of the external field and the internal field due to the presence of other magnetic molecules. As the inter-molecular magnetic couplings in these materials are weak compared to the intra-molecular interaction between the spins, it seems reasonable to consider the former as a perturbation. The purpose of this paper is to demonstrate that this argument fails in the case of LZS transitions. The point is that the LZS transition probability depends on the rate of change of the effective magnetic field at the crossing, which can be changed significantly by the presence of the internal magnetic field. The magnetization steps are found to be strongly affected by the type of interactions among molecules. We call this mechanism Feedback Effect on Magnetization Steps (FEMS). 

We first illustrate the effect for the case of the Mn<sub>12</sub>-acetate molecules. As a model Hamiltonian for this $`S=10`$ system we take 

$``$ $`=`$ $`D_1S_z^2D_4(S_x^4+S_y^4+S_z^4)`$ (2)   
$`ct\mathrm{sin}\theta S_x(ct\mathrm{cos}\theta +\lambda S_z)S_z.`$   
Compared to the model of  the extra feature in Hamiltonian (2) is the presence of a mean-field term, the strength of which we parametrize by $`\lambda `$. It is clear that in this mean-field approach any new effect appears as a result of global changes of the internal field generated by all the molecules and is not due to local fluctuations which should be treated separately .

Quantitative results for the zero-temperature non-equilibrium dynamics of model (2) can only be obtained through a numerical integration of the Schrödinger equation. Using standard techniques  we compute the magnetization steps for several values of $`\lambda `$. The results for $`D_1=0.64`$, $`D_4=0.004`$, tilt angle $`\theta =1^{}`$ and sweep rate $`c=0.001`$ (see , we use dimensionless units throughout this paper) are shown in Fig. 1.

It is clear that the dynamics of the internal field can change the size of the magnetization steps considerably. FEMS is observed for all $`\lambda 0`$. Note that the values of $`|\lambda |`$ we used are not unrealistic ($`|\lambda |D_4D_1`$), but rather small if we relate $`\lambda `$ to the dipole-dipole interaction which would yield a $`\lambda `$ which is $`10100`$ times larger.

At very low temperatures experiments  show steps at lower values of $`H`$ than the ones at which we observe steps in our calculation. In fact, for the set of model parameters given in (2) a much slower sweep rate $`c`$, much too slow for numerical calculations, is required if we want to study the effect of the internal field at all level crossings.

Therefore it is expedient to turn to a toy model inspired by the one used to describe Fe<sub>8</sub> . We take a $`S=2`$ model with the following Hamiltonian :

$`H`$ $`=`$ $`DS_z^2+E(S_x^2S_y^2)`$ (4)   
$`+\mathrm{\Gamma }S_x(ct+\lambda S_z)S_z,`$   
where we take $`D=1`$, $`E=0.08`$ and $`\mathrm{\Gamma }=0.08`$. These parameters are chosen such that we get two steps with a probability of about one half.

In Fig. 2 we show the magnetization during a sweep of the magnetic field, with a sweep rate $`c=0.01`$, for several values of $`\lambda `$. We see that the FEMS effect is large.

The transition probabilities are given in Table I. We clearly see a large change in the transition probabilities due to the presence of the internal field.

A deeper understanding of the origin of the FEMS effect can be obtained by considering the system of $`N`$ $`S=1/2`$ molecules described by the Hamiltonian

$$=\underset{i=1}{\overset{N}{}}\left[\mathrm{\Gamma }\sigma _i^xJ\underset{j>i}{\overset{N}{}}\sigma _i^z\sigma _j^z+ct\sigma _i^z\right],$$
(5)   
where $`c`$ is the sweep rate, $`\mathrm{\Gamma }`$ is the transverse field and $`J`$ determines the interaction strength between the molecules ($`|J|\mathrm{\Gamma }`$). For simplicity we consider couplings between $`z`$-components only and assume the coupling between the molecules to be the same. Since $`|J|`$ is small, we assume that we can make a mean-field-like approximation. The occurrence of FEMS does not depend on these simplifications (see below). This yields a Hamiltonian of a single molecule in a background field:

$$=\mathrm{\Gamma }\sigma _x(ct+\lambda \sigma _z)\sigma _z,$$
(6)   
where $`\lambda J`$ is an effective interaction. The system is prepared in the ground state, corresponding to a large negative time $`t`$, and the magnetic field is swept with constant velocity, until a large positive time is reached. Then, in the LZS case with $`\lambda =0`$, the transition probability is given by the well-known LZS formula $`p=1\mathrm{exp}(\pi \mathrm{\Gamma }^2/c)`$. For $`\lambda 0`$ we write the Schrödinger equation corresponding to (6) in component form:

$`iu^{}`$ $`=`$ $`\left(ct\lambda (2|u|^21)\right)u\mathrm{\Gamma }d,`$ (7)   
$`id^{}`$ $`=`$ $`\left(ct+\lambda (2|u|^21)\right)d\mathrm{\Gamma }u,`$ (8)   
where we also have the normalization condition $`|u|^2+|d|^2=1`$. From numerical simulations we (see below) find that the tunneling is suppressed (enhanced) by the presence of a feedback term with positive (negative) $`\lambda `$. This can be understood in terms of a changed effective sweep rate at the point of the transition. Because the effective magnetic field at the position of the molecule is given by $`ct+\lambda (2|u|^21)`$, the effective sweep rate would be $`c+\lambda d\sigma _z/dt`$.

If $`\lambda `$ is small but non-zero, the mean field term only contributes at the point of the crossing. So we look at a Taylor expansion around the point of the transition $`t_c`$ (to be determined later),

$$u(t)=u_0+u_1(tt_c)+𝒪((tt_c)^2),$$
(9)   
and a similar expression for $`d(t)`$. We insert this expansion in (7) and (8) and obtain

$`i\stackrel{~}{u}^{}(\stackrel{~}{t})`$ $`=`$ $`\stackrel{~}{c}\stackrel{~}{t}\stackrel{~}{u}(\stackrel{~}{t})\mathrm{\Gamma }\stackrel{~}{d}(\stackrel{~}{t}),`$ (10)   
$`i\stackrel{~}{d}^{}(\stackrel{~}{t})`$ $`=`$ $`\stackrel{~}{c}\stackrel{~}{t}\stackrel{~}{d}(\stackrel{~}{t})\mathrm{\Gamma }\stackrel{~}{u}(\stackrel{~}{t}),`$ (11)   
with $`\stackrel{~}{t}=tt_c`$, $`\stackrel{~}{c}=c+4\lambda \mathrm{}(u_0u_1^{})`$ is the renormalized sweep rate, and were $`\mathrm{}(u)`$ is denoting the real part of $`u`$. We define $`t_c`$ as the point at which $`ct+\lambda \sigma _z`$ changes sign, so

$$t_c=\frac{\lambda }{c}\left(12|u_0|^2\right).$$
(12)   
This enables us to write $`\stackrel{~}{u}_0=u_0`$ and $`\stackrel{~}{u}_1=u_1`$. To determine these constants we use Zener’s solution  and the properties of Weber functions. We find

$$|u_0|^2=\frac{\pi }{4}\delta e^{\pi \delta /4}\left|\frac{1}{\mathrm{\Gamma }(1+\frac{i\delta }{4})}\right|^2=\frac{1}{2}\left(1(1p)^2\right),$$
(13)   
where $`p`$ is the new probability for crossing, i.e. $`p=1\mathrm{exp}(\pi \mathrm{\Gamma }^2/\stackrel{~}{c})`$ and $`\delta =\mathrm{\Gamma }^2/\stackrel{~}{c}`$, and $`t_c=\lambda (1p)^2/c`$. The shift of the field at which the transition occurs can be written as $`\mathrm{\Delta }H=\lambda (1p)^2`$. To determine $`\stackrel{~}{c}`$ we calculate

$$\mathrm{}(u_0u_1^{})=\sqrt{\stackrel{~}{c}}\frac{\pi \delta }{2}e^{\delta \pi /4}\mathrm{}\frac{e^{i\pi /4}}{\mathrm{\Gamma }\left(1+\frac{i\delta }{4}\right)\mathrm{\Gamma }\left(\frac{1}{2}\frac{i\delta }{4}\right)}.$$
(14)   
We find that (14) can be approximated by

$$\mathrm{}(u_0u_1^{})\sqrt{\frac{\pi \stackrel{~}{c}}{8}}\delta e^{\delta \pi /4},$$
(15)   
with an error of maximally $`10\%`$ (see Fig. 3). Within this approximation, $`\stackrel{~}{c}`$ is given by the implicit equation

$$\stackrel{~}{c}c+\lambda \mathrm{\Gamma }^2\sqrt{2\pi /\stackrel{~}{c}}e^{\mathrm{\Gamma }^2\pi /4\stackrel{~}{c}}.$$
(16)   
A simple relation can be obtained by replacing $`\stackrel{~}{c}`$ by $`c`$ on the right hand side. Then

$$\stackrel{~}{c}c+\lambda \mathrm{\Gamma }^2\sqrt{2\pi /c}e^{\pi \mathrm{\Gamma }^2/4c},$$
(17)   
and

$$p1\mathrm{exp}\left(\frac{\pi \mathrm{\Gamma }^2}{c}\frac{1}{1+\lambda \mathrm{\Gamma }^2\sqrt{2\pi /c^3}e^{\mathrm{\Gamma }^2\pi /4c}}\right).$$
(18)   
The resulting probabilities are shown in Fig. 3. The resulting probabilities based on a numerical solution of (15) or (16) for $`\stackrel{~}{c}`$ show similar behavior. Also shown are the results obtained from the exact numerical solution of the Schrödinger equation (6). As a test of the validity of the mean-field approximation we also show the result of four interacting $`S=1/2`$ spins, where we assumed $`\lambda =(N1)J`$. Clearly the exact results confirm the validity of the mean-field approximation and the simple analytic expression (18).

For values of $`\lambda `$ below approximately $`2.0`$ the description in terms of a renormalized sweep rate breaks down, which can also be seen from the singularity in the argument of the exponent in eq. (18). This is because the picture of a simple, single crossing breaks down and the effective magnetic field at the position of the spin will no longer be a strictly increasing function of time. We conclude that the expression (18) captures the main features of FEMS at a single crossing.

The relevant parameters, controlling the size of FEMS, are $`\mathrm{\Gamma }/\sqrt{c}`$ and $`\lambda /\sqrt{c}`$. Only for S=1/2 the energy-level splitting is directly proportional to $`\mathrm{\Gamma }^2`$. For the high-spin molecules this is not case (see above), in particular for the levels with large $`|m|`$. Although in these cases the effective energy level-splitting that enters the approximate two-level description can be small, a rather small value of $`\lambda `$ can nevertheless change the transition probability significantly.

We have shown that the magnetization steps in the hysteresis loops of clusters of high-spin molecules may depend sensitively on the change of the internal magnetic field at these steps. This implies that the dynamics of this internal fields has to be incorporated in a description of the magnetization dynamics, even if its magnitude appears to be small compared to the other model parameters (for large spin). At finite temperatures the effect described in this paper will be enhanced further due to the thermalization to states with lower energy and larger magnetization .

We would like to thank W. Wernsdorfer for illuminating discussions. Support from the Dutch “Stichting Nationale Computer Faciliteiten (NCF)” and from the Grant-in-Aid for Research of the Japanese Ministry of Education, Science and Culture is gratefully acknowledged.