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# Role of dipolar and exchange interactions in the positions and widths of EPR transitions for the single-molecule magnets Fe8 and Mn12

## I Introduction

Single-molecule magnets (SMM’s) consist of identical molecules, each of which made up of several magnetic ions surrounded by many different species of atoms. A single molecule of the SMM’s Mn12-acetateLIS80  and Fe8WIEG84  has an effective ground-state spin of $`S=10`$ and a strong crystal-field anisotropy. A zero-field energy barrier against magnetization reversal is approximately 65 K (30 K) for uniaxial Mn12 (biaxial Fe8). BARR97 ; HILL98 ; PERE98 ; MIRE99 ; CACI98  Despite their large effective spin, these single-molecule magnets have shown quantum coherenceGARG93 ; GUNT95  and quantum tunneling between the energy levels of the two potential wells.GUNT95 ; VILL94 ; CHUD98  Although dipolar interactions between different molecules are weak, in the low-temperature limit and near zero applied field, a dipolar interaction could stimulate the quantum tunneling and thus explain the non-exponential magnetization relaxation observed at early times.PROK98 ; OHM98 ; CUCC99 ; WERN99 ; MIYA01 ; LIU01

Recently, electron paramagnetic resonance (EPR) experiments on single crystals of Fe8 and Mn12 have revealed interesting effects in the widths and positions of the EPR peaks as functions of energy level, resonance frequency, and temperature when the applied field is along the easy axis. HILL98 ; BLIN01 ; MACC01 ; PARK02 ; HILL02  For both Fe8 and Mn12, at fixed frequency, the linewidths increase with decreasing energy levels (the largest linewidth corresponding to the transition between the ground state and the first excited state), and for a particular transition the linewidths increase with decreasing frequency. On the other hand, the details of the temperature dependence of the linewidths for the two materials are quite different. For Mn12, the linewidths increase smoothly with increasing temperature, showing a rather weak temperature dependence. For Fe8, for transitions at low resonant fields, the linewidths increase sharply with temperature at low temperatures, reach a maximum, and then decrease slowly with temperature at higher temperatures. The exception is the transition associated with the ground state, for which the linewidth decreases with increasing temperature in the whole temperature range studied (2$``$50 K). On the other hand, for the transitions with high resonant fields, the linewidths increase monotonically with increasing temperature. For Fe8, the line positions change non-monotonically with energy level and temperature.

In Ref.PARK02, , which was our first attempt to understand the energy level and resonance frequency dependence of the linewidths, we showed that for both single crystals of Fe8 and Mn12 the distribution in the uniaxial anisotropy parameter $`D`$ of the single-spin Hamiltonian, caused by defects in the samples, contributes substantially to the inhomogeneous linewidths at constant temperature. This was also recently supported by terahertz spectroscopy for Mn12.PARKS01  The microscopic origin of the distribution in $`D`$ has not yet been fully understood.CHUD01 ; CORN01  The analysis further showed that for Fe8 the dipolar interactions between molecules contribute to the linewidths as significantly as the distribution in $`D`$, while for Mn12 their contribution is less significant.PARK02  In a recent millimeter-wave study on Fe8,MUKH01  the dipolar field may have been overestimated because the distribution in $`D`$ was not included.

Since the approximations made in Ref.PARK02,  reasonably well explained the linewidth behavior at fixed temperature, in the present paper we investigate the temperature dependence of the linewidths and line positions. To explain this additional feature, we take into account the inter-molecular spin-spin interactions (exchange and dipolar), as well as distributions in the uniaxial anisotropy parameter $`D`$ and the Landé $`g`$-factor. We find that the distributions in $`D`$ and $`g`$ do not contribute to shifts in line positions with temperature, but the exchange and dipolar interactions produce nonzero local fields which are temperature dependent (at low temperatures), so that they can make the line positions change with temperature. Thus, to explain the temperature dependence of the measured line shifts, both the exchange and dipolar interactions are needed. Without the exchange interaction, we cannot explain the observed non-monotonic line shifts with temperature. This was not included in our earlier study, Ref.PARK02, . Although the exchange interaction was not considered in our earlier study, its effect on the linewidths is negligible as long as the magnitude of the exchange constant is much smaller than the linewidths.AABB

This paper is organized as follows. A brief summary of the experimental procedures is presented in Sec. II. The models for Fe8 and Mn12 are described separately in Sec. III. Sec. IV describes our calculated linewidths and line shifts vs temperature, and their discussed in comparison with the experimental data. Our conclusions are provided in Sec. V.

## II Summary of Experimental Procedures

All of the EPR experiments were performed on single crystals with the magnetic field aligned along or close to the direction of the easy magnetization axis, in a temperature range from 2 K to 50 K. For Mn12, this direction coincides with that of the longest dimension of the essentially needle-shaped crystals. For Fe8, the direction was determined by measurement of the largest spread of the resonant field, by rotating the crystal around the approximately known orientation of the easy axis. The single crystals were prepared as described earlier.HILL98 ; PERE98 ; ACHE01-1 ; ACHE01-2 ; ACHE02  EPR measurements were made in the 100$``$190 GHz range with a resonant microwave cavity system described by Hill et al.HILL99 , which enables observation of distortion-free EPR line shapes. The linewidths were determined by computer-fitting of the observed experimental spectra to either a Gaussian or a Lorentzian function for the spectra obtained at various temperatures. All the spectra were obtained by keeping the frequency fixed and sweeping the field to obtain the resonance peaks, as is usual in EPR spectroscopy.DALA82

## III Model

For the examined single-crystal sample of Fe8,HILL02  there are two sources of the EPR line shifts: temperature dependence of $`D`$ and the electronic spin-spin interactions (dipolar and exchange interactions) between different molecules. There are also two sources of the EPR line broadening: the $`D`$-strain effect (distribution in $`D`$) and the spin-spin interactions.PARK02  For the examined Mn12 sample,HILL02  the sources of the line broadening are the $`D`$-strain, the $`g`$-strain,PILB  and the spin-spin interactions.PARK02

In our model, hyperfine interactions are not considered for the following reasons: (i) The observed line shifts and changes in the linewidths were much larger for Fe8 than for Mn12. (ii) On the other hand, hyperfine fields are orders of magnitude larger for Mn12 (in which all nuclei have spins of $`I=5/2`$) than for Fe8 (98% of Fe nuclei with $`I=0`$). (iii) Any residual effect of the hyperfine fields was included in background linewidths.

Possible mis-alignment of the external field and a spread in the in-plane fields are also not considered since mis-alignment of the external field cannot provide the temperature dependence of the linewidths and shifts. We checked that for Fe8 the effect of a distribution in the transverse anisotropy parameter $`E`$ on the linewidths was negligible. We also found that a spread in the in-plane fields (possibly caused by nuclear spins) can give rise to a distribution in the easy axis of each molecule, leading to asymmetries in EPR lineshapes.PARK02-2 ; PARK02-3

The model and technique used in this study are similar to those in Ref.PARK02, , except that we here take into account the non-spherical sample shapes and the actual crystal structures. Therefore, we here summarize them only briefly, focusing on what causes the temperature dependence of the line shifts and linewidths for each source. The temperature dependence of $`D`$ is discussed in Sec. IV A.1. In our convention, the energy level $`M_s=+10`$ is the ground state when the field is applied along the positive $`z`$ axis, while in Refs.MACC01, ; HILL02,  the ground state is $`M_s=10`$. For clarity, we discuss Fe8 and Mn12 separately.

### III.1 Fe8

We consider an effective single-spin Hamiltonian which satisfies approximate $`D_2`$ symmetry,

$`_0`$ $`=`$ $`DS_z^2E(S_x^2S_y^2)g\mu _BH_zS_z,`$ (1)
where the uniaxial anisotropy parameter $`D=0.288k_B`$, the transverse anisotropy parameter $`E=0.043k_B`$,MACC01  $`g`$ is the Landé $`g`$-factor which is close to 2, and $`\mu _B`$ is the Bohr magneton. Here $`S_\alpha `$ is the $`\alpha `$th component of the spin angular momentum operator, and $`H_z`$ is the longitudinal static applied magnetic field. We assume that the longitudinal magnetic field is applied along the easy axis (the $`z`$ axis), and we ignore the small transverse anisotropy terms ($`E`$ terms) in calculating the linewidths. Thus, the energy level $`M_s`$ is a good quantum number of the spin operator $`S_z`$. According to our convention, the ground state is $`M_s=+10`$.

Using the density-matrix equation BLUM  with the Hamiltonian, Eq. (1), and an interaction between the spin system and an oscillating transverse field, we calculate the power absorption between the levels $`M_s`$ and $`M_s1`$ for a fixed value of the uniaxial anisotropy parameter $`D`$. In the power absorption, the line-shape function includes a natural linewidth, which is a function of temperature. Next we calculate the average power absorption with a Gaussian distribution in $`D`$, where $`D`$ itself is assumed to be temperature independent. As a consequence, the line broadening due to the $`D`$-strain effect becomes weakly temperature dependent because of the temperature dependence of the natural linewidths. To calculate the natural linewidths, we use the strength of the coupling between the spin system and a surrounding phonon heat bath obtained in Ref.LEUE00-2, . For example, for $`M_s=+10`$, the order of magnitude of the natural linewidths is several to several tens of gauss at temperatures below several tens of kelvin, and the widths increase with decreasing $`M_s`$.

The spin-spin interactions are calculated separately with $`D`$ fixed, and then combined with the $`D`$-strain effect to obtain the total linewidths. At low temperatures, all energy levels are not equally populated, and the populations of the levels change with temperature according to the Boltzmann factor. Thus, the local field on a particular molecule caused by surrounding molecules changes with temperature. Therefore, the spin-spin interactions are mainly responsible for the temperature dependence of both the line shifts and the linewidths. AABB ; MCMI60  To calculate the line shifts and the line broadening due to the spin-spin interactions, we use a multi-spin Hamiltonian which commutes with $`_jS_j^z`$, where the sum runs over all molecules. Details of the technique can be found in Ref.MCMI60, .

$`^{\mathrm{t}ot}`$ $`=`$ $`{\displaystyle \underset{i}{}}[_{0i}+V_i(t)]+^{(1)},`$ (2)
$`^{(1)}`$ $``$ $`^{\mathrm{d}ipole}+^{\mathrm{e}xch},`$ (3)
$`^{\mathrm{d}ipole}`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{jk}{\overset{}{}}}A_{jk}(\stackrel{}{S}_j\stackrel{}{S}_k3S_j^zS_k^z),A_{jk}\left({\displaystyle \frac{\mu _0}{4\pi }}\right){\displaystyle \frac{(g\mu _B)^2}{2r_{jk}^3}}(3\zeta _{jk}^21),`$ (4)
$`^{\mathrm{e}xch}`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \underset{jk}{\overset{}{}}}J_{jk}\stackrel{}{S}_j\stackrel{}{S}_k,`$ (5)
where $`_{0i}`$ is the single-spin Hamiltonian for the $`i`$th molecule, the sum $`_i`$ runs over all molecules, and $`V_i(t)`$ is the interaction between the $`i`$th molecule and the oscillating transverse field. Here $`^{\mathrm{d}ipole}`$ is the dipolar interaction between the molecules, and $`\zeta _{jk}`$ are the direction cosines of the vector between molecules $`j`$ and $`k`$ ($`\stackrel{}{r}_{jk}`$) relative to the easy axis ($`z`$ axis). The sum $`_{jk}^{}`$ runs over all molecules, so that any two indices are not the same. $`^{\mathrm{e}xch}`$ is the isotropic exchange interaction between the spins of nearest-neighbor molecules where the exchange coupling constant $`J_{ij}`$ is $`J`$ if the $`i`$th and $`j`$th spins are nearest neighbors and zero otherwise. It is reasonable to assume that $`_iV_i(t)`$ is much smaller than the dipolar and exchange interactions, which again are much smaller than the sum of the single-spin Hamiltonians. Since the field is swept at constant frequency, the energy levels change with the sweeping field. We neglect slight changes of the energy levels during resonances and use $`H_{\mathrm{r}es}=(h\nu D(2M_s1))/g\mu _B`$, where $`\nu `$ is an EPR frequency, as the field $`H`$ in the spin Hamiltonian to calculate the energy levels for the particular resonance.

To calculate the $`\mathrm{}`$th moment of the resonant field deviation, we formulate the $`\mathrm{}`$th moment for a frequency sweep and then convert it to a field sweep. This is justifiable because we neglect the slight energy change caused by the change of the field during a resonance. The probability density function of the EPR frequency $`\nu `$ is given by

$`F_\nu (\nu )`$ $`=`$ $`{\displaystyle \frac{_n_n^{}^\mathrm{\Delta }\{\mathrm{exp}(_n/k_BT)\mathrm{exp}(_n^{}/k_BT)\}|n|_jS_j^x|n^{}|^2}{_n_n^{}^+\{\mathrm{exp}(_n/k_BT)\mathrm{exp}(_n^{}/k_BT)\}|n|_jS_j^x|n^{}|^2}},`$ (6)
where $`_n`$ is the energy eigenvalue of $`_j_{0j}+^{(1)}`$, $`|n`$ is the corresponding eigenvector, $`_n^{}^+`$ denotes the sum over all states $`|n^{}`$ such that $`_n^{}_n`$, and $`_n_n^{}^\mathrm{\Delta }`$ denotes the sum over all states for which $`h\nu _n^{}_nh(\nu +d\nu )`$. Using Eq. (6), we calculate the $`\mathrm{}`$th moment,

$`\nu ^{\mathrm{}}`$ $`=`$ $`{\displaystyle \frac{_n_n^{}^+(_n^{}_n)^{\mathrm{}}\{\mathrm{exp}(_n/k_BT)\mathrm{exp}(_n^{}/k_BT)\}|n|_jS_j^x|n^{}|^2}{_n_n^{}^+\{\mathrm{exp}(_n/k_BT)\mathrm{exp}(_n^{}/k_BT)\}|n|_jS_j^x|n^{}|^2}},\mathrm{}=1,2,\mathrm{},`$ (7)
where the temperature dependence of the linewidths is included through the Boltzmann factors, and the eigenvalues of $`^{(1)}`$ can contribute to $`(_n^{}_n)^{\mathrm{}}`$ and/or the Boltzmann factors. Assuming that the dipolar and exchange interactions, $`^{(1)}`$, are much smaller than the thermal energy, we expand the Boltzmann factor into

$`\mathrm{exp}\left[{\displaystyle \frac{_j_{0j}+^{(1)}}{k_BT}}\right]`$ $`=`$ $`\mathrm{exp}\left({\displaystyle \frac{_j_{0j}}{k_BT}}\right)\left[1{\displaystyle \frac{^{(1)}}{k_BT}}+\mathrm{}\right]`$ (8)
and consider only the first term on the right-hand side. In Ref.VANV48, , the Boltzmann factor was not included since the temperature of interest was quite high, so that all energy levels were equally populated. In our calculations, we use a mean-field approximation, so that the sums of $`A_{jk}`$ and $`J_{jk}`$ \[Eqs. (4) and (5)\] can be separated from the spin operators.

To compare with the measured line shifts, we calculate perturbatively the first moment, $`HH_{\mathrm{r}es}`$, where $`H_{\mathrm{r}es}`$ is the resonant field without the spin-spin interactions, and subtract from it the first moment at a reference temperature, 30 K. This reference temperature was chosen because at higher temperatures additional line shifts can be expected from the temperature dependence of $`D`$. The calculated line shifts to zero order in $`^{(1)}/k_BT`$ contain the exchange coupling constant $`J`$ and the effective dipole field $`\mathrm{\Delta }_{jk}A_{jk}/N`$ ($`N`$ is the number of molecules in the sample and the summation runs over all molecules) as variable parameters. This zero-order result in $`^{(1)}/k_BT`$ depends on $`J`$ and $`\mathrm{\Delta }`$ through the terms $`(_n^{}_n)`$ in Eq. (7). Since $`\mathrm{\Delta }`$ depends on the sample shape due to the field-induced net magnetization, Ewald’s methodEWAL21  is not sufficient to estimate its value in our case.

To compare with the measured linewidths, we need to calculate the second central moment, $`(HH)^2`$, which is equivalent to $`(HH_{\mathrm{r}es})^2(HH_{\mathrm{r}es})^2`$, where $`(HH_{\mathrm{r}es})^2`$ and $`(HH_{\mathrm{r}es})^2`$ are calculated perturbatively to zero order in $`^{(1)}/k_BT`$.MCMI60  The square root of the second central moment is proportional to the broadening due to the spin-spin interactions. The quantity $`(HH_{\mathrm{r}es})^2`$ includes the following six terms, $`_{ij}^{}J_{ij}^2`$, $`_{ij}^{}J_{ij}A_{ij}`$, $`_{ij}^{}A_{ij}^2`$, $`_{ijk}^{}J_{ij}J_{jk}`$, $`_{ijk}^{}J_{ij}A_{jk}`$, and $`_{ijk}^{}A_{ij}A_{jk}`$. The quantity $`(HH_{\mathrm{r}es})^2`$ includes three terms, $`(_{ij}^{}J_{ij})^2/N`$, $`(_{ij}^{}J_{ij})(_{ij}^{}A_{ij})/N`$, and $`(_{ij}^{}A_{ij})^2/N`$. Here $`_{ij}^{}`$ and $`_{ijk}^{}`$ run over all molecules with the constraint that no two indices in the summations may be the same, and $`J_{ij}`$ and $`J_{jk}`$ are nonzero for nearest-neighbor molecules only. The coefficients of the last three terms (the summations over three indices $`i`$, $`j`$, and $`k`$) in $`(HH_{\mathrm{r}es})^2`$ are the same as those of the three terms in $`(HH_{\mathrm{r}es})^2`$. To simplify the second central moment, we use the identities

$`{\displaystyle \frac{1}{N}}\left({\displaystyle \underset{ij}{\overset{}{}}}J_{ij}\right)^2`$ $`=`$ $`{\displaystyle \underset{ij}{\overset{}{}}}J_{ij}^2+{\displaystyle \underset{ijk}{\overset{}{}}}J_{ij}J_{jk},`$ (9)
$`{\displaystyle \frac{1}{N}}\left({\displaystyle \underset{ij}{\overset{}{}}}J_{ij}\right)\left({\displaystyle \underset{ij}{\overset{}{}}}A_{ij}\right)`$ $`=`$ $`{\displaystyle \underset{ij}{\overset{}{}}}J_{ij}A_{ij}+{\displaystyle \underset{ijk}{\overset{}{}}}J_{ij}A_{jk},`$ (10)
$`{\displaystyle \frac{1}{N}}\left({\displaystyle \underset{ij}{\overset{}{}}}A_{ij}\right)^2`$ $`=`$ $`{\displaystyle \underset{ij}{\overset{}{}}}A_{ij}^2+{\displaystyle \underset{ijk}{\overset{}{}}}A_{ij}A_{jk}.`$ (11)
Summations over four different indices do not appear in Eq. (11) because $`_{ij}^{}A_{ij}=N_{j1}A_{1j}`$ by translational invariance. We thus have only three undetermined terms, $`_{ij}^{}J_{ij}^2`$, $`_{ij}^{}A_{ij}^2`$, and $`_{ij}^{}J_{ij}A_{ij}`$ in the calculated second central moment. The exchange coupling constant $`J`$ could be determined from the line-shift analysis. The remaining two terms, $`_{ij}^{}A_{ij}^2`$ and $`_{ij}^{}J_{ij}A_{ij}`$, can, in principle, be calculated from the exact geometry of the system. However, in our study, we take the two terms as variable parameters, and compare their optimum values with the calculated values. Physical justification for this is provided in Sec. IV.A.2.

We fix the EPR frequency at $`\nu =116.9`$ GHz and vary the temperature from 4 K to 35 K for the linewidth analysis (2 K to 30 K for the line-shift analysis). We do not analyze the experimental data above 35 K because at higher temperatures excited states (effective spin $`S<10`$) might play a role. Only good-quality (high signal-to-noise ratio) experimental data were selected. For the line-shift analysis, the exchange constant $`J`$ and effective dipole field $`\mathrm{\Delta }`$ are varied, while for the linewidth analysis, $`\mathrm{\Gamma }_{ij}^{}A_{ij}^2/N`$, $`\mathrm{\Lambda }_{ij}^{}J_{ij}A_{ij}/N`$, and the standard deviation of $`D`$ are varied within experimentally acceptable ranges in order to fit the experimental data. Note that in Ref.PARK02,  the molecules of Fe8 were assumed to be distributed on a simple cubic lattice in a spherical sample. For spherical samples the value of $`\mathrm{\Delta }`$ is zero for all effective dipole distances. Thus only one parameter, either $`\mathrm{\Gamma }`$ or the effective dipole distance, sufficed in the linewidth analysis. The real samples, however, were not spherical. The Fe8 sample examinedHILL02  was a thin rhombic platelet with acute angle of about 60 degrees, edges of length 0.7 mm, and thickness 0.17 mm, and the molecules in Fe8 are distributed on a triclinic lattice. Therefore, we here use two fitting parameters ($`\mathrm{\Delta }`$ and $`\mathrm{\Gamma }`$) to consider the dipole-dipole distributions in the real experimental samples described above.

### III.2 Mn12

For Mn12 we consider an effective single-spin Hamiltonian which satisfies tetragonal symmetry,

$`_0`$ $`=`$ $`DS_z^2CS_z^4g\mu _BH_zS_z`$ (12)
with $`D`$$`=`$$`0.55k_B`$, $`C`$$`=`$$`1.17\times 10^3k_B`$, and $`g`$$`=`$$`1.94`$. BARR97  Here we consider the case in which the applied field is along the easy axis (the $`z`$ axis), and we neglect the small transverse fourth-order anisotropy term, $`S_x^4+S_y^4`$.

The technique is the same as for Fe8, except for the following: (i) The $`g`$-strain effect provides a weak temperature dependence to the linewidths, caused by the temperature dependence of the natural linewidths. (ii) The resonant field without the spin-spin interactions is modified to

$`H_{\mathrm{r}es}`$ $``$ $`{\displaystyle \frac{h\nu D(2M_s1)+C(4M_s^36M_s^2+4M_s1)}{g\mu _B}}.`$ (13)
(iii) To calculate the natural linewidths, we use the strength of the coupling between the spin system and a surrounding phonon heat bath from Ref.LEUE00-1, . (iv) Dipoles are distributed on a centered tetragonal lattice with sample dimensions $`1\times 0.15\times 0.05`$ mm3. (In Ref. PARK02, , the dipoles were assumed to be distributed on a body-centered cubic lattice, and the sample was assumed to be spherical.) (v) The easy anisotropy axis is along the long side of the needle-shaped sample. (vi) For Mn12 the measured line shifts are negligible compared to the measured linewidths, so that we do not have to consider the exchange interaction and the effective dipole field ($`J=0`$ and $`\mathrm{\Delta }=0`$, so $`\mathrm{\Lambda }=0`$). Thus, the second central moment $`(HH)^2`$, which is proportional to the measured linewidths, is identical to the second moment $`(HH_{\mathrm{r}es})^2`$.

To compare with the experimental data, the frequency is fixed at $`\nu =189.123`$ GHz, and the temperature is varied from 10 K to 40 K. Our analysis ends at 40 K because at higher temperatures excited states (effective spin $`S<10`$) might play a role. HENN97 ; GOME98 ; BARB98  Only EPR spectra of good quality were selected, and $`\mathrm{\Gamma }`$ and the standard deviations of $`D`$ and $`g`$ were varied within acceptable ranges in order to fit the experimental data.

## IV Results and Discussion

We show that the spin-spin interactions (dipolar and/or exchange interactions) alone determine the trend of the temperature dependence of the line shifts and the linewidths. From the line-shift analysis, we can estimate the orders of magnitude of the exchange interaction and the effective dipole field and obtain their signs. Using this information, we can also explain quantitatively the linewidths, including the $`D`$-strain and/or the $`g`$-strain effects which give rise to a strong $`M_s`$ dependence but weak temperature dependence of the linewidths. The spin-spin interactions contribute more to the linewidths for Fe8 than for Mn12, mainly because the $`D`$-strain effect is dominant over the spin-spin interactions for Mn12, while it is comparable with the spin-spin interactions for Fe8. This explains the different temperature behavior of the linewidths for Fe8 and Mn12. The set of parameter values which best explains the experimental data has some systematic theoretical uncertainties, which are difficult to calculate exactly.

### IV.1 Fe8

#### IV.1.1 line shifts

It is known that the value of the uniaxial anisotropy parameter $`D`$ may vary smoothly with temperature.PENR50  To gauge the importance of this effect, we first assume that $`D`$ has a temperature dependence such as Fig. 1(a). Then the line shift, $`H(T)`$$``$$`H`$($`T`$$`=`$30 K), becomes monotonically temperature dependent, as shown in Fig. 1(b). Comparing Fig. 1(b) with the experimental data in Fig. 2(a), we see that the monotonic temperature dependence of $`D`$ cannot by itself explain the complicated temperature dependence of the measured line shifts. It could presumably contribute together with other factors described below. However, we hereafter take $`D`$ as a temperature independent parameter, for the sake of simplicity and because the exact temperature behavior is not yet known. We also note that the distribution in $`D`$ does not change the line positions.

Next, we consider the effect of the spin-spin interactions between molecules on the measured line shifts. If we first ignore the exchange interaction and consider the dipolar interaction only for a spherical sample with dipoles distributed on a simple cubic lattice (which is the assumption made in Ref.PARK02, ), then the effective dipole field $`\mathrm{\Delta }`$ vanishes, so that there is no line shift to zero order in $`^{(1)}/k_BT`$. Higher-order corrections \[the second term in Eq. (8)\] provide a much smaller and qualitatively different temperature dependence from that seen in the measurements \[compare Fig. 3(a) with Fig. 2(a)\]. If we include a non-zero effective dipole field $`\mathrm{\Delta }`$ only in the zero-order calculation, then a negative effective dipole field moves the line shifts for all the transitions down below zero \[Fig. 3(b)\]. On the other hand, if we include an exchange interaction only in the zero-order calculation, then a ferromagnetic exchange interaction (negative $`J`$) moves the line shifts up above zero for all transitions except $`M_s=+10`$ \[Fig. 3(c)\]. In both cases, the calculated line shifts behave very differently from the measured shifts \[Fig. 2(a)\]. Therefore, we need to include both the effective dipole field and the exchange interaction in order to explain the measured line shifts. An inter-molecular exchange interaction was recently observed for the different types of single-molecule magnets, Mn4 and Mn4 dimer.WERN02  Since the effective dipole field $`\mathrm{\Delta }`$ depends on the sample shape due to the field-induced net magnetization, we do not use Ewald’s methodEWAL21  to estimate $`\mathrm{\Delta }`$ and thus leave it as a fitting parameter. For the exchange interaction, we assume that the coupling constant $`J_{ij}`$ is isotropic along the $`a`$, $`b`$, and $`c`$ directions of the triclinic unit cell (although in experimental samples the exchange interactions are highly anisotropic), so that the coordination number is 6. The optimum values of $`\mathrm{\Delta }`$ and $`J`$ are $`\mathrm{\Delta }_{\mathrm{o}pt}20`$ gauss and $`J_{\mathrm{o}pt}7`$ gauss ($``$ 1 mK) respectively. With these optimum values, the calculated line shifts \[Fig. 2(b)\] reproduce well the trends of the temperature dependence of the experimental data \[Fig. 2(a)\]. Figure 2(c) shows a direct comparison between theory and experiment for a few transitions.

The negative sign of the effective dipole field ($`\mathrm{\Delta }<0`$) indicates that dipoles are antiferromagnetically coupled. This result seems to be in conflict with the prediction that the dipolar Ising spin system with the same structure as Fe8 is ferromagnetically ordered.FERN00 ; MART01  However, as pointed out in Ref. MART01, , the energy difference between the ferromagnetic and antiferromagnetic states is so small that any neglected effects may shift the ground state to an antiferromagnetic state. The negative sign of the exchange coupling constant $`(J<0)`$ corresponds to ferromagnetic coupling between the effective spins of the molecules. Thus, if there exists any ordering for Fe8, then the ordering temperature should be estimated by considering both the exchange and dipolar interactions. The two interactions compete with each other, thereby reducing the possible ordering temperature to a lower value than the ordering temperature with only one of the two interactions considered.

Finally, we show the calculated line shifts with several other parameter values that are different from the optimum ones. If the effective dipole field and the exchange interaction both change signs, then the calculated line shift also changes its sign. If the sign of $`\mathrm{\Delta }`$ is opposite to the sign of $`J`$, then the magnitude of the calculated line shift for $`M_s=+10`$ is much smaller than those for the other transitions, which does not agree with the experimental data \[compare Fig. 3(d) with Fig. 2(a)\]. Figure 3(e) shows the calculated line shifts with $`J<J_{\mathrm{o}pt}`$ and $`\mathrm{\Delta }=\mathrm{\Delta }_{\mathrm{o}pt}`$. Figure 3(f) shows the calculated line shifts with $`J=J_{\mathrm{o}pt}`$ and $`\mathrm{\Delta }<\mathrm{\Delta }_{\mathrm{o}pt}`$. All three figures \[Figs. 3(d)-(f)\] are significantly different from Fig. 2(b) with the optimized values.

#### IV.1.2 linewidths

For Fe8 the distribution in $`D`$ and the spin-spin interactions contribute approximately equally to the inhomogeneous line broadening. Figure 4 shows the calculated line broadening due to the $`D`$-strain effect only as a function of temperature at $`\nu =116.9`$ GHz. Here the standard deviation of the Gaussian distribution in $`D`$, $`\sigma _D`$, is approximately $`0.0064D`$. The line broadening caused by the $`D`$-strain only becomes temperature dependent, because the natural linewidths depend on temperature. The distribution in $`D`$ makes each molecule subject to a slightly different resonant field. A measured line shape is a sum of many Lorentzian line shapes with a natural linewidth and different resonant fields. We can calculate the variance of the resonant field, $`\sigma _D(2M_s1)/g\mu _B`$, due to the distribution in $`D`$ from the expression for $`H_{\mathrm{r}es}`$. If the natural linewidths are comparable with the variance of the resonant field, then the effect of temperature is significant. If the natural linewidths are much smaller than the variance, then the effect of temperature is negligible. The natural linewidth at 10 K (35 K) varies from 7 G (29 G) to 79 G (235 G) as $`M_s`$ changes from +10 to +3, using the parameter values in Ref.LEUE00-2, . The variance of the resonant field, $`\sigma _D(2M_s1)/g\mu _B`$, varies from 260 G to 70 G as $`M_s`$ is varied from +10 to +3 with $`\sigma _D=0.0064D`$. Thus, we find that for small $`M_s`$ the natural linewidths are comparable with the variance, while for large $`M_s`$ the natural linewidths are much smaller than the variance. Therefore, for small $`M_s`$ the calculated linewidths show a substantial temperature dependence, while for large $`M_s`$ there is only a very weak temperature dependence (see Fig. 4).

In Fig. 5 the calculated line broadening caused solely by the spin-spin interactions at fixed $`D`$ is shown vs temperature at $`\nu =116.9`$ GHz. Here we use the exchange constant, $`J=7`$ gauss, which was estimated from the measured line shifts (Sec. IV A.1), $`\mathrm{\Gamma }_{ij}^{}A_{ij}^2/N=86`$ gauss2, and $`\mathrm{\Lambda }_{ij}^{}J_{ij}A_{ij}/N=156`$ gauss2. For the ground state $`M_s=+10`$, the linewidths decrease with increasing temperature in the whole examined temperature range. For $`M_s=+9,+8`$, and +7, the widths first increase sharply with temperature at low temperatures, and then decrease slowly with temperature at high temperatures. For $`M_s=+6,+5,+4`$, and +3, the widths increase with increasing temperature in the whole examined temperature range. As the temperature increases, the $`M_s`$ dependence of the line broadening due to the spin-spin interactions decreases. This trend was also seen in the experimental linewidths (shown as symbols in Fig. 6), confirming that the spin-spin interactions are essential to understanding the temperature dependence of the linewidths.

The trends of the temperature dependence can be qualitatively understood through the relative magnitude difference of the thermal energy and the Zeeman energy splitting between the states $`M_s=+10`$ and $`M_s=10`$. If the Zeeman energy splitting is much larger than the thermal energy (this occurs at low temperatures), then the system is polarized. Thus, higher temperature provides larger populations in higher energy levels within the same potential well where the ground state is located. This leads to an increase in the randomness of the spin orientation so that linewidths become larger with increasing temperature. If the Zeeman energy splitting is much smaller than the thermal energy (this occurs at high temperatures), then some energy levels in both potential wells are populated. In this case, thermal fluctuations increase rapidly with increasing temperature, so that the duration time of the local magnetic field due to neighboring molecules becomes shorter than the spin-spin relaxation time $`T_2`$ (the inverse of the natural linewidths). Eventually, at very high temperatures the local field is averaged out. Therefore, the linewidths decrease with increasing temperature, which usually occurs in paramagnetic materials with very small or zero single-ion anisotropy.LARS89  (This effect is called motional narrowing.AABB ) Therefore, the “crossover” temperature where the maximum of the linewidth occurs must be proportional to the Zeeman energy splitting between $`M_s=+10`$ and $`M_s=10`$, which is $`2g\mu _BH_{\mathrm{r}es}10`$. For example, for the transition $`M_s=+10+9`$ at $`\nu =116.9`$ GHz, the resonant field is less than 0.1 T, so the Zeeman splitting is about 2$`k_B`$. Consequently, its crossover temperature is below the examined temperature range. The crossover temperature increases with decreasing $`M_s`$ because the resonances are observed at increasing fields for decreasing $`M_s`$. For the transitions $`M_s=+9+8,+8+7`$, and $`+7+6`$, the crossover temperatures are within the examined temperature range (see the inset in Fig. 6 of Ref.HILL02, ). For $`M_s=+6,+5,+4`$, and +3, the crossover temperatures are above the studied temperature range.

Figure 6 shows the experimental data (symbols), and our calculated linewidths (curves), including both the $`D`$-strain effect and the spin-spin interactions with $`\sigma _D0.0064D`$, $`J=7`$ gauss, $`\mathrm{\Gamma }=86`$ gauss2, and $`\mathrm{\Lambda }=156`$ gauss2. (The spread in $`D`$ here is different from that reported in Ref.PARK02, , because $`\sigma _D`$ is sample dependent and the samples examined were different. The value of $`\mathrm{\Gamma }`$ corresponding to an effective dipole distance of 12 Å (Fe8) in Ref.PARK02,  was about 203 gauss2.) As shown in Fig. 6, our calculated linewidths agree well with the experimental data, except in the low-temperature range for large $`M_s`$ transitions ($`M_s=+10,+9,+8`$). The experimental linewidths for $`M_s=+10`$ show $`1/T`$ dependence in the whole examined temperature range.PPHMF  For $`M_s=+10,+9`$, and +8, the calculated linewidths are appreciably smaller than the experimental linewidths below 10 K. As a possible explanation for this discrepancy, we speculate that at low temperatures and large $`M_s`$, (i) our assumption, $`^{(1)}/k_BT1`$, may break down, and/or (ii) there might be other linewidth contributions that we have neglected, which should be included along with the dipolar and exchange interactions. In principle, when $`^{(1)}/k_BT`$ is not much smaller than unity, a first-order calculation in $`^{(1)}/k_BT`$ produces corrections of $`𝒪(1/k_BT)`$. But its implementation is quite complicated, and a first-order calculation may anyway not be sufficient to explain fully the measured linewidths.

Introducing the concept of the crossover temperature to explain the temperature dependence of the widths seems to be successful for $`\nu =116.9`$ GHz. However, recent EPR experiments (Fig. 8 in Ref.HILL02, ) showed that even when the frequency increased to $`\nu =145.9`$ GHz such that the resonant field for the ground state transition ($`M_s=10`$) is approximately 1 tesla, the linewidths for this transition still increased with decreasing temperatures down to 2 K. This cannot be explained using the reasoning given above, because the crossover temperature for the transition is approximately 15 K, so that the linewidths should decrease with decreasing temperature below about 15 K. At present, we do not fully understand the broadening of this ground-state transition. (At $`\nu =145.9`$ GHz, for other transitions than the ground-state transition, the temperature dependence of the linewidths can be understood using the concept of the crossover temperature.)

Consideration of exchange interaction in the linewidths slightly reduces $`\sigma _D`$ (from 0.0076D to 0.0064D) and the dipolar interaction (from $`\mathrm{\Gamma }=103`$ gauss2 to $`\mathrm{\Gamma }=86`$ gauss2). However, the quality of the linewidth fit including exchange interaction is comparable to that without exchange interaction since the exchange coupling constant is very small compared with the linewidths.AABB  The two fitting parameters, $`\mathrm{\Gamma }=86`$ gauss2, and $`\mathrm{\Lambda }=156`$ gauss2, can be calculated using the exact geometry of the system. The calculated values are $`\mathrm{\Gamma }_{\mathrm{c}al}=500`$ gauss2 and $`\mathrm{\Lambda }_{\mathrm{c}al}=137`$ gauss2, when the easy axis is 9 off from the $`a`$ axis toward the positive $`b`$ axis, and 7 off from the $`ab`$ plane.WERN02-2  The optimum value of $`\mathrm{\Lambda }`$ is quite close to $`\mathrm{\Lambda }_{\mathrm{c}al}`$, in contrast with $`\mathrm{\Gamma }`$. Possible reasons that the optimum value of $`\mathrm{\Gamma }`$ is much smaller than $`\mathrm{\Gamma }_{\mathrm{c}al}`$ are as follows: (i) In our calculation, we considered each molecule to be a point dipole. If we consider the atomic positions of the eight Fe ions in each molecule and calculate the dipolar interaction between Fe ions in different molecules, then the sum of the squared dipolar interaction, $`\mathrm{\Gamma }`$, can be significantly reduced. (ii) Recent NMR experiments for the single-molecule magnet Mn12 showed some spin-density leakage onto the ligands.ACHE01-1 ; ACHE01-2 ; ACHE02  This indicates indirectly that for Fe8 the spin density in a single molecule may not be confined only on the core, which would thus reduce the magnetic moments of the eight Fe ions. The above two reasons are our speculations to explain the discrepancy, but it is still unclear why considering the atomic structure within each molecule does not substantially change the value of $`\mathrm{\Lambda }`$.

### IV.2 Mn12

The experimental data for Mn12 are limited to resonance frequencies below 190 GHz, so that the large $`M_s`$ transitions where the line shifts are significant cannot be observed for these low-frequency measurements. Additionally, the linewidths for Mn12 are an order of magnitude larger than those for Fe8. Therefore, relatively small line shifts are probably masked for Mn12. Thus, hereafter, the small line shifts are ignored in our analysis, so the exchange interaction and the effective dipole field $`\mathrm{\Delta }`$ need not be considered in the linewidth analysis for Mn12. The sources of the line broadening are then $`D`$-strain, $`g`$-strain, and the dipolar interaction.

Line broadening caused by the $`D`$-strain and $`g`$-strain effects for Mn12 is found to have a weak temperature dependence (not shown), which is similar to the line broadening due to the $`D`$-strain effect for Fe8. The contribution of the dipolar interaction to the linewidths is shown vs temperature in Fig. 7. Here $`\mathrm{\Gamma }_{ij}^{}A_{ij}^2/N=203`$ gauss2. The dipolar broadening increases with increasing temperature for $`M_s=+6,+5,+4,+3`$, and $`+2`$. We do not see the regime where the dipolar broadening decreases with increasing temperature, because the crossover temperature for $`M_s=+6`$, about 32 K (the resonant field is about 1.6 T), is close to the highest temperature analyzed (40 K). Unlike Fe8, the $`M_s`$ dependence of the dipolar broadening does not decrease with increasing temperature (the curves are almost parallel). This is also observed in the experimental data (shown as symbols in Fig. 8).

We combine the three effects ($`D`$-strain, $`g`$-strain, and dipolar interactions) to find that the calculated linewidths agree well with the measured linewidths with $`\sigma _D0.018D`$, $`\sigma _g0.002g`$, and $`\mathrm{\Gamma }=203`$ gauss2, as shown in Fig. 8. (The value of $`\mathrm{\Gamma }`$ corresponding to an effective dipole distance of 14 Å for Mn12 in Ref.PARK02,  turned out to be the same as that obtained for Fe8 in Ref. PARK02, .) Here the standard deviation of $`g`$ is quite small, so that we cannot rule out the possibility of $`\sigma _g=0`$. Note that $`\sigma _D`$ and $`\sigma _g`$ vary from sample to sample. The optimum parameter values found here are different from those estimated in Ref.PARK02, , because the examined Mn12 sample was different. The calculated value for $`\mathrm{\Gamma }`$, with the exact geometry of Mn12 from Ref.LIS80,  (with each molecule considered as a point dipole), is $`\mathrm{\Gamma }_{\mathrm{c}al}=397`$ gauss2; this is, again, quite a bit higher than the optimum value for $`\mathrm{\Gamma }`$, probably for the same reasons as for Fe8 although the origin of this discrepancy remains unclear. Overall, the temperature dependence of the linewidths for Mn12 is weaker than for Fe8, because the distribution in $`D`$ for Mn12 is roughly three times as wide as for Fe8, and the dipolar broadening for Fe8 is comparable to that for Mn12. Thus, the distribution in $`D`$ conceals the significant temperature dependence of the dipolar broadening for Mn12.

As a consistency check, we also used the same values of the three parameters ($`\sigma _D0.018D`$, $`\sigma _g0.002g`$, and $`\mathrm{\Gamma }=203`$ gauss2) to analyze the measured linewidthsHILL02  as functions of the energy level $`M_s`$ for several frequencies ($`\nu =127.8,148.5,169,181.8`$, and 189.1 GHz) at a fixed temperature (T=20 K). Our calculated linewidths are in good agreement with the experimental data as shown in Fig. 9. Due to a dominant contribution of the distribution in $`D`$ to the linewidths, the linewidths do not depend much on the resonance frequency.

## V Conclusion

We have investigated how the EPR line shifts and linewidths vary with temperature for different energy levels $`M_s`$ with the applied field along the easy axis for the single-molecule magnets Fe8 and Mn12. Our calculations consider the spin-spin interactions between molecules, as well as distributions in $`D`$ and $`g`$. We have found that the distributions in $`D`$ and $`g`$ provide a weak temperature dependence to the linewidths, and that the spin-spin interactions (exchange and dipolar interactions) dominate the temperature dependence of the line shifts and the linewidths. For Fe8, the line-shift analysis (Figs. 2 and 3) provides possible evidence of an exchange interaction between molecules, and it determines the sign and order of magnitude of the exchange interaction. The competition of the suggested exchange interaction with the dipolar interaction would tend to lower a possible magnetic ordering temperature. A small exchange interaction does not affect the linewidth analysis significantly because the exchange coupling constant is much smaller than the typical linewidths. Table 1 summarizes the optimized values of the parameters used in our analysis. Those parameters are, in principle, independent of the resonance frequencies, but some of them are expected to be somewhat batch and shape dependent, as indicated in Table 1. Because of the much broader distribution in $`D`$ for Mn12, the linewidths for Fe8 show a stronger temperature dependence than those for Mn12. This conclusion also corroborates our assumption that $`D`$ is distributed for both materials,PARK02  although the microscopic origin of this spread is not yet well understood.CHUD01 ; CORN01

## Acknowledgments

This work was funded by NSF Grant Nos. DMR-9871455, DMR-0120310, DMR-0103290, and DMR-0196430, Research Corporation (S.H.), and by Florida State University through the School of Computational Science and Information Technology and the Center for Materials Research and Technology.


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# Split Instability of a Vortex in an Attractive Bose-Einstein Condensate

## Abstract

An attractive Bose-Einstein condensate with a vortex splits into two pieces via the quadrupole dynamical instability, which arises at a weaker strength of interaction than the monopole and the dipole instabilities. The split pieces subsequently unite to restore the original vortex or collapse.

Quantized vortices in gaseous Bose-Einstein condensates (BECs) offer a visible hallmark of superfluidity Matthews ; Madison ; Abo , where repulsive interatomic interactions play a crucial role in the vortex stabilization and lattice formation. Attractive BECs, on the other hand, cannot hold vortices in any thermodynamically stable state. A fundamental issue of the decay of a many-particle quantum system may be addressed if a vortex is created in an attractive BEC. Such a state has become possible owing to the development of the Feshbach technique Inouye  by which the strength and the sign of interactions can be controlled Cornish ; Roberts01 ; Donley .

Suppose that a singly quantized vortex is created in a BEC with repulsive interaction and that the interaction is adiabatically changed from repulsive to attractive. According to previous work Dalfovo , the vortex state remains metastable until a dimensionless strength of interaction $`g`$ to be defined later reaches a critical value $`g_M^{\mathrm{cr}}(<0)`$, and when $`|g|`$ exceeds $`|g_M^{\mathrm{cr}}|`$, the system develops a monopole (breathing-mode) instability and collapses. In this Letter, we show that this conclusion holds only when the system has exact axisymmetry, and that even an infinitesimal symmetry-breaking perturbation induces the quadrupole dynamical instability that appears for $`|g|`$ smaller than $`|g_M^{\mathrm{cr}}|`$. We note that similar dynamical instabilities Recati ; Sinha ; Tsubota  initiate vortex nucleation observed by the ENS group Madison . A dynamical instability is also shown to transfer a vortex from one to the other component of a binary BEC system Garcia00 . Here, we show that yet another dynamical instability causes a vortex to split into two pieces that revolve around the center of the trap. Surprisingly, in some parameter regimes, the pieces subsequently unite to restore the original vortex, and this split-merge cycle repeats. We report below the results of our studies on the collapsing dynamics of a vortex in an attractive BEC.

We first investigate the Bogoliubov spectrum of a single-vortex state. The single-vortex state is determined so as to minimize the Gross-Pitaevskii (GP) energy functional within the axisymmetric functional space $`\psi _0=f(r,z)e^{i\varphi }`$ with $`r=(x^2+y^2)^{1/2}`$, where we ignore the effect of vortex bending Rosen ; Garcia01 ; bending . In the following analysis, we normalize the length, time, and wave functions in units of $`d_0(\mathrm{}/m\omega _{})^{1/2}`$, $`\omega _{}^1`$, and $`(N/d_0^3)^{1/2}`$, where $`\omega _{}`$ is the radial trap frequency, and $`N`$, the number of BEC atoms. We obtain the Bogoliubov spectrum by numerically diagonalizing the Bogoliubov-de Gennes equations Edwards

$`\left(K+2g|\psi _0|^2\right)u_n+g\psi _0^2v_n`$ $`=`$ $`E_nu_n,`$ (1a)
$`\left(K+2g|\psi _0|^2\right)v_n+g\psi _0^2u_n`$ $`=`$ $`E_nv_n,`$ (1b)
where $`K^2/2+(r^2+\lambda ^2z^2)/2\mu `$ with $`\lambda \omega _z/\omega _{}`$, and $`n`$ is the index of the eigenmode. Here, $`g4\pi Na/d_0`$ characterizes the strength of interaction, where $`a`$ is the s-wave scattering length. For a vortex state $`\psi _0e^{i\varphi }`$, each angular momentum state $`u_ne^{im\varphi }`$ is coupled only to $`v_ne^{i(m2)\varphi }`$, and we shall refer to $`m`$ as the angular momentum of the excitation.

We find that there is at least one negative eigenvalue in the $`m=0`$ mode for any $`g<0`$ and $`\lambda `$ even in the presence of a rotating drive. The vortex state with attractive interactions is therefore thermodynamically unstable, and eventually decays into the non-vortex ground state by dissipating its energy and angular momentum. At sufficiently low temperatures in a high-vacuum chamber, however, the thermodynamic instability is irrelevant, since the energy and angular momentum are conserved. In fact, recent experiments Madison  have demonstrated that the vortex state in a stationary trap has a lifetime of $`1`$ s, which is much longer than the characteristic time scales of the dynamics that we shall discuss below.

When the complex eigenvalues emerge in the Bogoliubov spectrum, the amplitude of the corresponding mode grows exponentially in time. As noise is inevitable in experimental situations, such dynamical instabilities are more important than the thermodynamic one at low temperature.

Figure 1 shows the real and imaginary parts of the lowest eigenvalues of the $`m=1`$ and $`3`$ excitations in an isotropic trap.

The eigenvalues become complex at the critical strength of interaction $`g_Q^{\mathrm{cr}}=15.06`$, showing the onset of the dynamical instability in the quadrupole mode. The imaginary part of the complex eigenvalue is proportional to $`\sqrt{g_Q^{\mathrm{cr}}g}`$ as shown in the inset in Fig. 1. The complex eigenvalues emerge also in the dipole modes, i.e., $`m=0`$ and $`2`$, for $`g<g_D^{\mathrm{cr}}=18.02`$. The eigenvalues with other $`m`$ are real for $`g`$ larger than the critical value for the monopole (radial-breathing-mode) instability $`g_M^{\mathrm{cr}}=23.7`$.

Figure 2 shows the $`\lambda `$ dependence of $`g_Q^{\mathrm{cr}}`$, $`g_D^{\mathrm{cr}}`$, $`g_M^{\mathrm{cr}}`$, and $`g_{\mathrm{nonvortex}}^{\mathrm{cr}}`$ in axi-symmetric traps, where $`g_{\mathrm{nonvortex}}^{\mathrm{cr}}`$ is the critical value for the non-vortex state to collapse through the monopole instability.

We note that $`|g_M^{\mathrm{cr}}|`$ is always larger than $`|g_Q^{\mathrm{cr}}|`$ and $`|g_D^{\mathrm{cr}}|`$, and hence the latter instabilities arise before the monopole instability sets in. For a trap with $`\lambda 0.3`$, the quadrupole instability arises before the dipole one, unlike the quasi-1D toroidal trap Rokhsar ; Ueda ; Berman .

We also performed numerical diagonalization for 2D systems. Strong confinement in the $`z`$ direction produces the quasi-2D trap, when $`\mathrm{}\omega _z`$ is much larger than the characteristic energy of the dynamics. The effective strength of interactions in the quasi-2D oblate trap is given by $`g^{2\mathrm{D}}=\sqrt{\lambda /(2\pi )}g^{3\mathrm{D}}`$ Castin . In the 2D system, the dynamical instability arises in the quadrupole, dipole, and monopole modes at $`g_Q^{2\mathrm{D}\mathrm{c}\mathrm{r}}=7.79`$, $`g_D^{2\mathrm{D}\mathrm{c}\mathrm{r}}=11.48`$, and $`g_M^{2\mathrm{D}\mathrm{c}\mathrm{r}}=23.4`$. The dependencies of the complex eigenvalues on $`g`$ are similar to that in Fig. 1.

To understand the dynamical instabilities analytically, let us consider the GP action integral in 2D

$$S=𝑑t𝑑𝐫\psi ^{}\left(i\frac{}{t}\frac{^2}{2}+\frac{r^2}{2}+\frac{g}{2}|\psi |^2\right)\psi .$$
(2)
We assume that the state evolution is described by $`\psi =_mc_m(t)\varphi _m(𝐫)`$, where $`\varphi _m(𝐫)`$ is assumed to take the form of $`\varphi _m(𝐫)=[r^{|m|}/(\sqrt{\pi |m|!}d^{|m|+1})]\mathrm{exp}[r^2/(2d^2)+im\varphi ]`$ and $`d=[1+g/(8\pi )]^{1/4}`$ minimizes the GP energy functional for the $`m=1`$ state. Substituting this $`\psi `$ into Eq. (2) and minimizing $`S`$ with respect to $`c_m`$ yields

$$i\dot{c}_m=\epsilon _mc_m+g\underset{mm_1m_2m_3}{}G_{m_2,m_3}^{m,m_1}c_{m_1}^{}c_{m_2}c_{m_3},$$
(3)
where $`\epsilon _m𝑑𝐫(|\psi _m|^2+r^2|\psi _m|^2)/2`$ and $`G_{m_3,m_4}^{m_1,m_2}𝑑𝐫\psi _{m_1}^{}\psi _{m_2}^{}\psi _{m_3}\psi _{m_4}`$. When the BEC exists in the $`m=1`$ mode, we obtain $`c_1(t)=e^{i\mu t}+O(|c_{m1}|^2)`$ with $`\mu =1/d^2+d^2+g/(4\pi d^2)`$. The linear analysis of Eq. (3) for $`\stackrel{~}{c}_me^{i\mu t}c_m`$ $`(m1)`$ yields

$$i\dot{\stackrel{~}{c}}_m=(\epsilon _m\mu )\stackrel{~}{c}_m+2G_{m,1}^{m,1}\stackrel{~}{c}_m+G_{1,1}^{m,2m}\stackrel{~}{c}_{2m}^{}.$$
(4)
It follows from this that, for $`m=1`$, the eigenfrequencies are given by $`A\pm \sqrt{B}`$, where $`A[g/(8\pi )1]/[1+g/(8\pi )]^{1/2}`$ and $`B3+5g/(8\pi )+[1+g/(2\pi )g^2/(32\pi ^2)]/[1+g/(8\pi )]`$. We find that $`B`$ is a monotonically increasing function for $`g>8\pi `$, and $`B`$ becomes negative for $`g<g^{\mathrm{cr}}9.2`$, which is in reasonable agreement with $`g_Q^{2\mathrm{D}\mathrm{c}\mathrm{r}}=7.79`$ stated above. We also find that the imaginary part appearing for $`g<g^{\mathrm{cr}}`$ is proportional to $`\sqrt{g^{\mathrm{cr}}g}`$, in agreement with the inset of Fig. 1.

The Bogoliubov analysis described above is valid only if deviations from a stationary state are small. To follow further evolution of the wave function, we must solve the time-dependent GP equation. Since we are studying the growth of small perturbations, high precision is required in the numerical integration, and hence we consider the GP equation in 2D

$$i\frac{\psi }{t}=\left[\frac{1}{2}^2+\frac{1}{2}r^2+g^{2\mathrm{D}}|\psi |^2\right]\psi $$
(5)
to ensure sufficiently small discretization in the Crank-Nicholson scheme Ruprecht . This situation corresponds to an oblate trap with large $`\lambda `$.

Figures 3 (a)-(f) depict the time evolution of the density and phase profiles with $`g^{2\mathrm{D}}=9`$, which is smaller than the critical value for the quadrupole mode $`g_Q^{2\mathrm{D}\mathrm{c}\mathrm{r}}=7.79`$ but larger than that for the dipole mode $`g_D^{2\mathrm{D}\mathrm{c}\mathrm{r}}=11.48`$.

A small symmetry-breaking perturbation is added to the initial state to imitate noise in realistic situations. Due to the quadrupole instability, the vortex is first stretched \[Fig. 3 (b)\], and then splits into two clusters that revolve around the center of the trap \[Fig. 3 (d)\] with angular velocity $`0.73\omega _{}`$. In the first deformation process the $`m=1`$ and $`3`$ components grow exponentially, and their Lyapunov exponents agree with the imaginary part of the complex eigenvalues. Interestingly, the split process is reversible: the two clusters subsequently unite to restore the ring shape \[Fig. 3 (f)\], and this split-merge process repeats. We numerically checked that no split-merge phenomenon occurs for $`g^{2\mathrm{D}}>g_Q^{2\mathrm{D}\mathrm{c}\mathrm{r}}`$, where the system is metastable. The insets in Fig. 3 illustrate the phase plots. At $`t=16`$, there are three topological defects: the central one exists from the outset, and the other two enter as the vortex splits, in accordance with the fact that the $`m=3`$ component grows upon the vortex split. The two side vortices cannot be seen in the density plot, and hence they may be called “ghost” vortices Tsubota  that carry very little angular momentum.

The two clusters in Fig. 3 (d) may be regarded as revolving “solitons” whose phases differ by $`\pi `$. In fact, at an energy only slightly below that of Fig. 3 (d), there is a low-lying state in which two solitons revolve without changing their shapes. It is interesting to note that this situation is similar to the soliton-train formation observed by the Rice group Strecker , where the modulation (dynamical) instability causes a quasi-1D condensate to split into solitons when the interaction is changed from repulsive to attractive using the Feshbach resonance. We note that similar instabilities split an optical vortex propagating in a nonlinear medium into spiraling solitons Tikhonenko ; Garcia\_opt ; Mihalache . This similarity between attractive BECs and optical solitons Stegeman  implies that other nonlinear phenomena, such as pattern formation, which has been predicted in attractive BECs Saito , may also be realized in optical systems.

When the system becomes too small to be observed by the in situ imaging method due to the attractive interaction, the condensate must be expanded before imaging. Figure 3 (g) shows the expanded image at $`t=17`$, where the interaction is switched from $`g^{2\mathrm{D}}=9`$ to $`g_{\mathrm{expand}}=50`$ and the trapping potential is switched off at $`t=16`$ \[Fig. 3 (d)\]. The image shows the interference fringes due to the overlap of the atomic clouds emanating from the two clusters. The wavelength of the interference pattern is proportional to the expansion time. Figure 3 (h) shows the expanded image at $`t=18`$ with $`g_{\mathrm{expand}}=0`$. Comparing Figs. 3 (g) and (h), we find that the stronger repulsive interaction produces more fringes and bends them around the center.

When $`|g^{2\mathrm{D}}|`$ exceeds $`|g_D^{2\mathrm{D}\mathrm{c}\mathrm{r}}|=11.48`$, a dipole instability arises in addition to the quadrupole one. The dipole instability causes atoms to transfer from one cluster to the other, thereby inducing the collapse.

Figures 4 (a)-(c) show the collapse process with $`g^{2\mathrm{D}}=11.5`$. After the split-merge process repeats a few times, the balance between the two clusters is broken due to the dipole instability. As a consequence, the cluster labeled A grows \[Fig. 4 (a)\], then B grows \[Fig. 4 (b)\] like a seesaw, and eventually B absorbs most atoms and collapses \[Fig. 4 (c)\], where the original topological defect begins to spiral out as indicated by the white arrow in the inset. With a stronger attractive interaction $`g^{2\mathrm{D}}=12`$, both clusters collapse immediately after the vortex split as shown in Figs. 4 (d)-(f). In this collapse process, we found the exchange of a vortex-antivortex pair (see the insets). This phenomenon is also seen in the split-merge process with $`g^{2\mathrm{D}}=11.5`$, while it is not seen at weaker attractive interactions, say, at $`g^{2\mathrm{D}}=9`$.

Figures 4 (g)-(i) show the collapse where the interaction is switched from $`g^{2\mathrm{D}}=0`$ to $`g^{2\mathrm{D}}=24<g_M^{2\mathrm{D}\mathrm{c}\mathrm{r}}`$ at $`t=0`$. The vortex first shrinks due to the monopole instability \[(g) $``$ (h)\], then splits into two clusters due to the quadrupole instability \[(h) $``$ (i)\], and both clusters collapse. When the interaction is switched to an even greater attractive one, a shell structure is formed Saito , which splits into several parts due to multipole instabilities, and each fragment collapses and explodes Donley , producing very complicated collapsing dynamics.

In conclusion, we have studied the dynamical instabilities of a quantized vortex in an attractive BEC. The dynamical quadrupole instability spontaneously breaks the axisymmetry and splits a vortex into clusters that revolve around the center of the trap, which then unite to restore the vortex or eventually collapse. The dynamical instabilities presented here play a much larger role than the thermodynamic one at low temperature, and serve as a dominant mechanism for the collapsing dynamics of a rotating condensate: vortices collapse via the dynamical instabilities around the topological defects.

This work was supported by a Grant-in-Aid for Scientific Research (Grant No. 11216204) by the Ministry of Education, Science, Sports, and Culture of Japan, and by the Toray Science Foundation.


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# Chiral Born-Infeld Theory: topological spherically symmetrical solitons

## 1 Introduction

The concept of the baryon as a chiral soliton has a long history. The idea of a unified theory for baryons and mesons that is formulated in terms of chiral field was only proposed for the first time by Skyrme . The well-known Skyrme Model is used for analyzing static properties of barions, for describing nucleon-nucleon forces, meson-nucleon scattering and for many other low-energy aspects of baryons and mesons physics.

In the seventies ’t Hooft and Witten  have shown that, in the limit $`N_c\mathrm{}`$, QCD can be reformulated in terms of effective meson theory like Skyrme Model and that chiral solitons of such theory reproduce the static properties of real baryons. These facts attracted special attention to the theories with chiral solitons.

Effective meson field theory can be formulated in terms of chiral field $`U=\mathrm{exp}(i\frac{\stackrel{}{\varphi }_\pi \stackrel{}{\tau }}{f_\pi })`$ where the vector field $`\stackrel{}{\varphi }_\pi `$ is associated with $`\pi `$ \- mesons and $`f_\pi =93`$ MeV is the pion decay constant. The simplest chiral invariant prototype lagrangian for mesons field $`\stackrel{}{\varphi }_\pi `$ is given by

$$_{pr}=\frac{f_\pi ^2}{4}\mathrm{Tr}L_\mu L^\mu ,$$
(1)
where $`L_\mu =U^+_\mu U`$ is a Cartan left-invariant form (see reviews ). However using the scale transformation analogous to the Derrick Theorem  one can find that theory with the lagrangian (1) has no finite energy static solutions and all models with chiral soliton appear to be various modifications of the prototype lagrangian. For example, the skyrmeon (chiral soliton ofthe Skyrme Model) exists due to the including of the Skyrme-part $`\mathrm{\Delta }_{Sk}=\mathrm{Tr}[L_\mu ,L_\nu ]^2/e^2`$ in lagrangian of this model. This theory has a set of topological static solutions and one can classify these solutions by the value of the topological (baryon) charge

$$B=\frac{1}{24\pi ^2}d^3ϵ_{ijk}\mathrm{Tr}(L_iL_jL_k).$$
(2)
In this model such solutions are associated with baryon states with different baryon charges, and soliton with $`B=1`$ (skyrmeon) is treated as a nucleon. Such kind of solutions and quantum fluctuations about them is well studied now (see ) and results of such analysis are in agreement with the experiment data with accuracy of 30-40 percents for baryonic masses and another static properties of baryons.

But there are many other ways for stabilization of chiral soliton, because from the methodological point of view, arising of the Skyrme part in the lagrangian of effective meson field theory is an ”ad hoc” procedure, and there are no real physical bases for this procedure. Of course, one can treat this part in the effective lagrangian as a leading high derivative expansion of effective chiral meson action (see review ), but this approach leads to numerous questions so far. Two most important ones concern the physical nature of the scale parameter ($`e`$) in this theory and the influence of another terms of expansion on existence and stability of chiral solitons.

Another possible way of stabilizing of chiral solitons was suggested in . In these works the role of the vector ($`\rho `$) and pseudo-scalar ($`\omega `$) mesons in chiral soliton physics is discussed. Procedure of $`\omega `$-stabilization leads to forming of topological soliton solution. Many other procedures of stabilization were proposed so far. One such approach that allows to get over the difficulty connected with scale instability of chiral solitons in 3+1 dimension was proposed in . Indeed, prototype lagrangian (1) has well-known stable static topological solitons in 1+1 dimension . This situation stems from the fact of dimensionless of the chiral action in 1+1 dimension. By analogy with 1+1 dimension case, in  the model with the lagrangian

$$_{3/2}=\frac{f_\pi ^2}{4}(\mathrm{Tr}L_\mu L^\mu )^{3/2},$$
(3)
was considered. The authors of  name this model Born-Infeld-Skyrme Model because of the half-integer power in expression (3).

In  another type of a Born-Infeld-Skyrme Model with the lagrangian

$$_{SkBI}=\frac{f_\pi ^2}{4}\mathrm{Tr}L_\mu L^\mu +\beta ^2\left(\sqrt{1+\frac{1}{16e^2\beta ^2}\mathrm{Tr}[L_{\mu ,},L_\nu ]^2}1\right)$$
(4)
was proposed. This model satisfies the basic requirements for models of Born-Infeld type and have stable soliton solution, but the Born-Infeld part in the lagrangian (4) plays the role of Skyrme-term in the lagrangian (3) and this model is one possible modification of Skyrme’s procedure.

The consistent effective low-energy meson’s theory construction is a very complicated task that is closely connected to the quark’s confinement problem and to the problem of spontaneous breaking of chiral symmetry. It is desirable that such theory should be Lorentz and chiral invariant and should have a set of finite energy stable solutions. In the case of electro-magnetic fields such kind of an effective low-energy theory is the well-known Born-Infeld model . In this work we study the direct analogue of the Born-Infeld action for chiral fields. By construction our model has no singular solutions and looks very attractive as a possible effective action for mesons fields. This model has a set of stable topological solitons. These solutions can be treated as baryons states in our model. The physical motivation of our model is beyond the scope of this article.

In Section 2, we discuss the problem of constructing of a Born-Infeld (BI) action for the chiral field (ChBI model). The lagrangian and equation of motion are presented. The spherically symmetrical configurations of chiral field are considered and topological spherically symmetrical solitons are studied. In Section 3 we summarise the results of this paper.

## 2 The Born-Infeld theory for Chiral Fields

In the well-known paper , Born and Infeld proposed a non-linear covariant action for electro-magnetic fields with very attractive features. Firstly, in the framework of BI theory the problem of singular self-energy of electron can be solved. In this theory the electron is a stable finite energy solution of the BI field equation with electric charge. Second, the BI action has a scale parameter $`\beta `$. Using expansion by this parameter one reduces the BI action to the usual Maxwell form in the low-energy limit.

We want to perform a very similar procedure with the chiral prototype lagrangian (1). Like in the case of BI action, our chiral model must have a set of finite energy solutions with integer values of charge (topological or baryon), and in the low-energy limit such a theory must reproduce the prototype lagrangian (1). The model must be Lorentz and chiral invariant. Finally, the form of such theory follows from the analogy with the action of a relativistic particle, the BI action for EM and YM field. This form has geometrical nature and corresponds to a number of analogies between chiral dynamics, gauge theory and general relativity .

Arguing as above, let us consider a theory with lagrangian

$$_{ChBI}=f_\pi ^2\mathrm{Tr}\beta ^2\left(1\sqrt{1\frac{1}{2\beta ^2}L_\mu L^\mu }\right)\frac{f_\pi ^2}{4}\mathrm{Tr}L_\mu L^\mu ,$$
(5)
where $`\beta `$ is a mass dimensional scale parameter of our model. It is easily shown that the expansion of the lagrangian (5) gives us the prototype theory as the leading order theory by parameter $`\beta `$. Our theory contains only second-order derivative terms. Thus the dynamics of this field theory can be studied in detail.

Now we consider the spherically symmetrical field configuration

$$U=e^{iF(r)(\stackrel{}{n}\stackrel{}{\tau })},\stackrel{}{n}=\stackrel{}{r}/|r|.$$
(6)
The energy of such field configuration is the functional

$$E^\beta [F]=8\pi f_\pi ^2\beta ^2\underset{0}{\overset{\mathrm{}}{}}\left(1R\right)r^2𝑑r,$$
(7)
where

$$R=\sqrt{1\frac{1}{\beta ^2}\left(\frac{F^2}{2}+\frac{\mathrm{sin}^2F}{r^2}\right)}.$$

Using the variation principle, we get the equation of motion

$$\left(r^2\frac{F^{}}{R}\right)^{}=\frac{\mathrm{sin}2F}{R}$$
(8)
and for amplitude $`F(r)`$ we obtain

$$(r^2\frac{1}{\beta ^2}\mathrm{sin}^2F)F^{\prime \prime }+(2rF^{}\mathrm{sin}2F)$$

$$\frac{1}{\beta ^2}(rF^3F^2\mathrm{sin}2F+3\frac{1}{r}F^{}\mathrm{sin}^2F\frac{1}{r^2}\mathrm{sin}2F\mathrm{sin}^2F)=0.$$
(9)
The next aim of our investigation is finding the solutions of equation (9).

Equation (9) is a very complicated nonlinear differential equation. In order to solve it, only numerical or approximation methods seem applicable. The crucial point of such analysis is that the leading derivative term in this equation contains the factor

$$\mathrm{\Phi }[F](r)=\left(r^2\frac{1}{\beta ^2}\mathrm{sin}^2F\right).$$
(10)
If there exits $`r_00`$ such that $`F(r_0)=\pm \mathrm{arcsin}(\beta r_0)`$, then it is easily shown that $`F^{}(r)|_{r=r_0}=0`$. But if $`r_0=0`$, then $`F(0)=\pi N`$ where $`N𝐙`$ and $`F^{}(r)|_{r=0}=a0`$. Using the standard procedure, one obtains the asymptotic behavior near this point ($`r=0`$, $`F(0)=\pi N`$)

$$F(r)=\pi N+ar\frac{7a^24\beta ^2}{30(a^2\beta ^2)}a^3r^3+\underset{¯}{O}(r^5),$$
(11)
where $`a^2<\beta ^2/3`$ is a constant. Of course, the derivative at the point $`r=R`$ is not zero.

To guarantee the stability of our solutions we should choose the following asymptotics at infinity ($`r\mathrm{}`$)

$$F(r)=b(1/r)^2\frac{b^3}{21}(1/r)^6\frac{b^3}{3\beta ^2}(1/r)^8+\underset{¯}{O}(1/r^{10}),$$
(12)
where $`b`$ is a constant. Solutions with such asymptotics at infinity and with asymptotics (11) ($`N0`$) are stable because vacuum states $`F(0)=\pi N`$ and $`F(\mathrm{})=0`$ are different.

Notice that equation (9) has very useful symmetries. First of all, this equation is symmetrical with respect to the changes $`FF+N\pi ,N𝐙`$ and $`FF`$.

The numerical investigation of the solutions of equation (9) which have the asymptotics (12) ($`b>0`$) at infinity is presented in Fig.1. Most of such solutions can be evaluated only for $`r>r_0`$, where $`r_0`$ is determined by $`F(r_0)=\pm \mathrm{arcsin}(\beta r_0)`$. But among this set of solutions there are solutions with $`r_0=0`$. Such solutions have the asymptotics (11) at origin, and these are the topological solitons of the ChBI theory. The topological charge is defined by integral (2) as usual. Solitons with $`B=1,2`$ and $`3`$ are presented in Fig.2. The scale parameter $`\beta =807\text{MeV}`$ is defined from the hypothesis that the soliton with $`B=1`$ is a nucleon. Indeed, using now a scale transformation in (7), one gets

$$\beta =\frac{8\pi f_\pi ^2}{m_p}E(B=1,\beta =1)=807\text{MeV},$$
(13)
where $`E(B=1,\beta =1)=3.487`$ is the energy of this soliton solution for $`B=1`$ and $`\beta =1`$.

In conclusion of this section let us consider the question about the asymptotics of energy of spherically symmetrical solitons at $`B\mathrm{}`$. In case of the Skyrme Model $`E(B)B^2`$ . In the Chiral-Born-Infeld’s case it is not so. In Table 1 the values of the energy $`E(B,\beta =1)`$ for $`B=1\mathrm{}10`$ are presented.

It is easily shown that the Table 1 data can be interpolated by the expression

$$E(B,\beta =1)1.0625B^3+1.8755B^2+0.473B+0.233.$$
(14)
This interpolation is shown in Fig.3 where dots are the data from Table 1.

## 3 Conclusions

The aim of this paper is to construct a Born-Infeld theory for chiral fields. This theory has no singular solution and so the Chiral Born-Infeld theory is a good candidate on the role of effective chiral theory. In our work we show that this theory has the stable cluster finite-energy solution. In the concept of a unified theory of mesons and baryons  such solutions are treated as the baryon states.

Of course, we do not give a comprehensive investigation of the Born-Infeld theory. The questions about non-spherical solutions, quantum fluctuations about such solutions and corresponding properties of baryons or about the nucleon-nucleon interaction are not clear now. But maybe the most important question in such investigation is about physical substantiation of such theory. All of these questions should be the themes for a future investigation.

In conclusion I would like to draw attantion to another class of solutions that were studied in Section 2. These solutions are defined everywhere, except the little ($``$ 0.2 fm) spherical region about the origin. These solutions look like a ”bubble” of vacuum in the chiral fields and are of interest for the chiral bag model of baryons . This question should be the theme for a future investigation too.