# Many-Spin Effects and Tunneling Properties of Magnetic Molecules

## Abstract

Spin tunneling in molecular magnets has attracted much attention, however theoretical considerations of this phenomenon up to now have not taken into account the many-spin nature of molecular magnets. We present, to our knowledge, the first successful attempt of a realistic calculation of tunneling splittings for Mn<sub>12</sub> molecules, thus achieving a quantitatively accurate many-spin description of a real molecular magnet in the energy interval ranging from about 100 K down to 10<sup>-12</sup> K. Comparison with the results of the standard single-spin model shows that many-spin effects affect the tunneling splittings considerably. The values of ground state splitting given by single-spin and many-spin models differ from each other by a factor of five.

Progress in coordination chemistry lead recently to synthesis of a completely new class of magnetic materials of nanometer size, molecular magnets, which has drawn the attention of physicists as well as chemists . In particular, these materials have been proven to be very suitable for the study of mesoscopic quantum tunneling effects in magnetic materials. A number of impressive experimental results have been obtained recently, such as the thermally-induced tunneling , ground state - to - ground state tunneling and topological phase effects in spin tunneling .

Among others, the molecular magnet $`\mathrm{Mn}_{12}\mathrm{O}_{12}(\mathrm{CH}_3\mathrm{COO})_{16}(\mathrm{H}_2\mathrm{O})_4`$ (below referred to as Mn<sub>12</sub>) constitutes a subject of great interest. The effect of resonant magnetization tunneling has been first observed and studied in detailed experiments on Mn<sub>12</sub> , and, at present, a substantial amount of reliable experimental data has been collected. However, progress in understanding the properties of molecular magnets is greatly hampered by the lack of a comprehensive theoretical description. Recent experiments  show that the conventional single-spin description of magnetic molecules, including Mn<sub>12</sub>, does not accurately describe their properties and the constituent many-spin nature of these molecules should be taken into account. This can be particularly important for understanding tunneling properties; for which it has been demonstrated  that the single-spin description of a many-spin system can give totally misleading results for tunneling splittings, differing by three orders of magnitude from exact values.

Therefore, the development of an adequate many-spin description of molecular magnets constitutes an important theoretical problem, which becomes especially complicated if the tunneling properties are to be studied. For example, the magnetic cluster of Mn<sub>12</sub> molecule consists of eight ions Mn<sup>3+</sup> with spin 2 and four Mn<sup>4+</sup> ions with spin 3/2 (see Fig. 1), coupled by anisotropic interactions, so that the Hilbert space of the corresponding spin Hamiltonian consists of 10<sup>8</sup> levels. Furthermore, the tunneling splittings in Mn<sub>12</sub> are very small, of order of 10<sup>-12</sup> Kelvin. Obviously, the brute-force direct calculation of tiny tunneling splittings, even for several low-lying states, is far beyond the capabilities of modern computers. Although several methods have been developed to cope with this problem , we are not aware of any calculations of tunneling splittings made for realistic models of complex molecular magnets, so that the possibility of such a simulation has not been demonstrated yet.

In this paper, we present, to our knowledge, the first successful attempt to calculate the tunneling splitting for a realistic model of Mn<sub>12</sub> , thus explicitly showing the possibility of calculating tunneling splittings in rather complex molecular magnets. As a result, we achieve a quantitatively accurate many-spin description of a real system in the energy interval ranging from about 100 K down to 10<sup>-12</sup> K, covering 14 orders of magnitude.

The 8-spin model, which forms a basis for present calculations, has been described and discussed thoroughly in Ref. . The central idea of the model is to use the natural hierarchy of interactions present in Mn<sub>12</sub>. Namely, the antiferromagnetic exchange interactions $`J_1220`$ K (see Fig. 1) between ions Mn<sup>3+</sup> and Mn<sup>4+</sup>  are significantly stronger than other isotropic exchange ($`J_2`$, $`J_3`$ and $`J_4`$) and anisotropic interactions, so at low temperatures they can be considered as absolutely rigid. In other words, the spins of the corresponding ions can be considered as forming dimers with a total rigid spin 1/2. The validity of this model has been supported by megagauss-field experiments : the states of dimers with the spin higher than 1/2 (excitations of dimers) come into play when the external magnetic field is about 400 T. The same conclusion can be drawn from the the dependence of the magnetic susceptibility of Mn<sub>12</sub> versus temperature (see, e.g. Ref. ).

After consideration of different possible interactions, the following spin Hamiltonian has been proposed in Ref.  to describe Mn<sub>12</sub> molecules:

$``$ $`=`$ $`J\left({\displaystyle \underset{i}{}}𝐬_i\right)^2J^{}{\displaystyle \underset{k,l}{}}𝐬_k𝐒_lK_z{\displaystyle \underset{i=1}{\overset{4}{}}}\left(S_i^z\right)^2`$ (2)   
$`+{\displaystyle \underset{i,j}{}}𝐃^{i,j}[𝐬_i\times 𝐒_j].`$   
Here, $`𝐒_i`$ and $`𝐬_i`$ are the spin operators of large spins $`S=2`$ and small dimer spins $`s=1/2`$, correspondingly, where the subscript $`i`$ denotes the index of the spin. Isotropic exchange between small spins and large spins is described by the parameter $`J^{}`$, whereas $`J`$ denotes the exchange of small spins with each other. The third term describes the single-ion uniaxial anisotropy of large spins. Finally, the fourth term describes the antisymmetric Dzyaloshinsky-Morya (DM) interactions in Mn<sub>12</sub>, and $`𝐃^{i,j}`$ is the Dzyaloshinsky-Morya vector describing DM-interaction between $`i`$-th small spin and $`j`$-th large spin. The molecules of Mn<sub>12</sub> possess the fourfold rotary-reflection axis (the symmetry $`C_4`$), which imposes restrictions on the DM-vectors $`𝐃^{i,j}`$, so that Dzyaloshinsky-Morya interactions can be desribed by only three parameters $`D_xD_x^{1,8}`$, $`D_yD_y^{1,8}`$, and $`D_zD_z^{1,8}`$.

The model discussed above has been demonstrated to describe correctly the energy spectrum up to about 100 K . It has allowed explaination of a wide range of experimental data, such as the unexpected splitting of neutron scattering peaks , results of EPR experiments  and measurements of magnetic susceptibility versus temperature . This model has provided a quantitative description of the response of Mn<sub>12</sub> molecules to the transversal magnetic field  (external field applied perpendicular with respect to the easy axis of the molecule). The following set of the parameters has been determined for the spin Hamiltonian (2):

$`J=3.6\text{ K},J^{}=84\text{ K},K_z=5.69\text{ K}`$ (3)   
$`D_x=25.3\text{ K},D_y=0.6\text{ K},D_z=2.0\text{ K}.`$ (4)   
Having this model at hand, can we describe correctly the tunneling properties of Mn<sub>12</sub>?

In the Hamiltonian (2), only the fourth term, representing Dzyaloshinsky-Morya interactions, allows for tunneling. Indeed, the first two terms (describing isotropic exchange interactions) conserve both the total spin of the molecule $`𝒮`$ and its projection $`𝒮_z`$ (the $`z`$-axis is chosen to coincide with the $`C_4`$ axis of the molecule). Thus, these terms can not lead to tunneling between the levels with different $`𝒮_z`$. The third term, representing an easy-axis anisotropy, also conserves this quantity. Therefore, even though the levels $`|𝒮_z=+M`$ and $`|𝒮_z=M`$ are degenerate, in the absense of the Dzyaloshinsky-Morya term no tunneling between them can appear. But the DM-interaction mixes levels with different $`𝒮_z`$, thus giving rise to tunneling of the molecule’s spin. Below, for simplicity, we will denote the energy levels by the value of $`𝒮_z`$. Although it is not an exact quantum number in the system under consideration, we can formally consider the DM-interaction as a perturbation, and use perturbation theory terminology.

The first question to pose concerns the precision of the level splitting calculation. Parameters of the Hamiltonian are determined with some finite precision, and a small error (say, of the order of several Kelvin) affects the level energy by an amount of order of Kelvin, which is much larger than the very small value of tunneling splitting (of order of 10<sup>-12</sup> K). Does it deprive the calculational results of all meaning? To answer this question, we note that the levels $`|𝒮_z=+M`$ and $`|𝒮_z=M`$ are degenerate due to exact symmetry properties of the spin Hamiltonian, and, in the absense of the DM-term, would be degenerate at any values of parameters. Therefore, the tunneling splittings $`\mathrm{\Delta }E_{+M,M}`$ are governed only by the strength of the interaction which breaks the symmetry, i.e. DM-interaction. Therefore, if the parameters of the Hamiltonian are determined with reasonably small relative error, and if the simulation is done with sufficient accuracy, then the relative error of the level splittings will also be small. The results of our calculations confirm this conclusion.

In the calculation scheme we employed , the most significant error comes from the fact that only a fraction of all the levels produced by the spin Hamiltonian (2) are used in the calculations, and the influence of levels having higher energy is neglected. Therefore, to achieve reasonable accuracy, a sufficiently large number of levels should be taken into account. We studied the dependence of the resulting tunneling splittings $`\mathrm{\Delta }E_{+M,M}`$ for different pairs of degenerate levels $`|𝒮_z=+M`$ and $`|𝒮_z=M`$ on the number of lowest levels actually used in calculations. The results are shown on Fig. 2. It can be seen that the reasonable accuracy can be achieved by accounting for about the 700 lowest levels.

Final results for the tunneling splittings $`\mathrm{\Delta }E_{+M,M}`$ are presented in the Table, where the values obtained in many-spin calculations are compared with those given by the single-spin model. It is important to mention that the tunneling splittings should be zero for the levels with odd values of $`M`$ (i.e., $`|𝒮_z=\pm 9`$, $`|𝒮_z=\pm 7`$ etc.) because the fourfold symmetry of the molecule imposes certain restrictions on the symmetry of the spin Hamiltonian and makes some matrix elements vanish. In the single-spin model of Mn<sub>12</sub> this property of the spin Hamiltonian is introduced explicitly, by retaining only those operators which possess the required fourfold symmetry. In the many-spin simulations, we obtain the same result independently: the energies of the levels $`|𝒮_z=\pm M`$ for odd $`M`$ are the same with the accuracy of order of 10<sup>-28</sup> K, i.e. of order of computational error. This value is much less than the smallest of the splittings $`\mathrm{\Delta }E_{+10,10}=2.0310^{12}`$ K.

Analyzing the results presented in the Table, we see that the single-spin and many-spin models give rather close results for higher energy levels $`M=\pm 2`$ and $`M=\pm 4`$. It has been shown  that these values of tunneling splittings allow to describe the experimental data available now with a good precision. On the other hand, for the ground-state levels $`M=\pm 10`$ the single-spin model predicts the value of tunneling splitting five times larger than the many-spin model. The possibility of such a difference has been predicted before , and, to our knowledge, Mn<sub>12</sub> is the first example of a real system where this difference has been found. Unfortunately, reliable experimental data concerning ground state - to - ground state tunneling in Mn<sub>12</sub> are absent, so the single-spin and many-spin models can not be distinguished on the basis of experimental results. Nevertheless, many-spin consideration can be important for a correct quantitative description of the ground state - to - ground state tunneling in other molecular magnets, such as Fe<sub>8</sub>. Many-spin effects may be one possible explanation for the disagreement found in Ref.  between the experimental results and predictions of the single-spin model.

Summarizing, we evaluated the tunneling splittings in Mn<sub>12</sub> on the basis of the realistic many-spin model. We demonstrated that even tiny energy splittings, of order of 10<sup>-12</sup> K, can be calculated with reasonable precision for a rather complex molecular magnet. The results obtained have been compared with predictions of the single-spin model. We found that both models give close values for splittings of higher levels. Thus, the models can not be distinguished on the basis of experimental results available now, which provide the information only about upper levels splittings  ($`M=\pm 4`$ and $`M=\pm 2`$). However, the ground state splittings calculated using these two models differ by a factor of five. This difference may be important also for other molecular magnets, such as Fe<sub>8</sub>, where the ground state splitting given by the single-spin model is three times less than the value obtained in experiment.

This work was carried out at the Ames Laboratory, which is operated for the U. S. Department of Energy by Iowa State University under Contract No. W-7405-82 and was supported by the Director for Energy Research, Office of Basic Energy Sciences of the U. S. Department of Energy.