# Ising cubes with enhanced surface couplings

## I Introduction

In the thermodynamic limit, critical phenomena may occur not only in the bulk of a system, but also at its surfaces, edges and corners. To be specific, let us consider Ising magnets with short-range interactions. Then, there are two typical scenarios: (a) bulk, $`m_b`$, surface, $`m_1`$, edge, $`m_2`$, and corner, $`m_3`$, magnetizations may order at the same temperature (”ordinary transition”), but with different power–laws, and (b) surface, edge and corner magnetizations may order simultaneously first (”surface transition”) due to enhanced, strong surface couplings, followed by ordering of the bulk magnetization at the lower bulk transition temperature (”extraordinary transition”). Surface singularities at ordinary and surface transitions have been studied extensively, theoretically  as well as experimentally . Most of the rather few studies on edge critical behavior dealt with the ordinary transition . Only very recently, edge criticality both at the surface transition  and at the normal transition  has been investigated.

Similarly, corner criticality in three-dimensional Ising systems has been analysed, to our knowledge, only at the ordinary transition, applying mean-field theory  and Monte Carlo simulations . However, that case deserves to be studied at the surface transition as well for various reasons. For magnetic properties of nanostructured materials, corners are expected to play an important role . In addition, magnetic couplings may be enhanced at surfaces, especially at step-edges and corners . Last, but not least, the problem is of genuine theoretical interest. At the surface transition, the critical fluctuations are essentially two–dimensional. Edges are local perturbations acting then like defect lines in two-dimensional Ising models leading to interesting non–universal critical phenomena . Accordingly, corners, say, of an Ising cube may be interpreted as intersection points of three defect lines. At such points, one also expects intriguing non-universal behavior of local quantities, such as the corner magnetization, following exact analytical work on two–dimensional Ising systems with intersecting defect lines .   

## II Model, method and results

We study nearest–neighbor Ising models on simple cubic lattices with $`L\times M\times N`$ spins (usually we shall consider Ising cubes, i.e. $`L=M=N`$) and ferromagnetic interactions. The Hamiltonian may be written in the form

$``$ $`=`$ $`{\displaystyle \underset{bulk}{}}J_bS_{xyz}S_{x^{}y^{}z^{}}{\displaystyle \underset{surface}{}}J_sS_{xyz}S_{x^{}y^{}z^{}}`$ (2)   
$`{\displaystyle \underset{edgesurface}{}}J_{es}S_{xyz}S_{x^{}y^{}z^{}}{\displaystyle \underset{edge}{}}J_eS_{xyz}S_{x^{}y^{}z^{}}`$   
where the sums run over bonds between neighboring spins, $`S_{xyz}=\pm 1`$, with coupling constants to be specified below; $`x(y,z)`$ going from 1 to $`L(M,N)`$. Free boundary conditions hold for the spins in the surface planes. The pairs of neighboring spins in the Hamiltonian (1) are located either on edge sites with the edge coupling $`J_e`$, on edge and surface sites coupled by $`J_{es}`$, on surface sites with the interaction $`J_s`$, or on sites with at least one of the spins in the interior of the system interacting with the bulk coupling $`J_b`$. We refrained from assigning another coupling strength to pairs of spins on corner and edge sites, which is taken to be equal to $`J_e`$.

To study the behavior at the surface transition, $`T_s`$, we chose $`J_s=2J_b`$, where $`k_BT_s/J_b4.975`$ , while the bulk transition, $`T_c`$, occurs at $`k_BT_c/J_b4.5115`$ . The effect of the edge couplings was studied by considering the three cases (i) of equal surface couplings, i.e. $`J_e=J_{es}=J_s`$, (ii) of reduced edge couplings, especially $`J_{es}=J_s`$, $`J_e=J_b`$, and (iii) of reduced edge–surface couplings, especially $`J_e=J_s`$, $`J_{es}=J_b`$.

The size of the Ising cubes wih $`L^3`$ spins ranged from $`L=5`$ to $`L=80`$. In the Monte Carlo simulations, we used the efficient single–cluster–flip algorithm. Thermal averages were obtained from an ensemble of at least $`10^2`$ realizations, using different random numbers. In each realization, several $`10^4`$ clusters were taken into account, after equilibration.

The quantity of main interest is the corner magnetization, or more general, the local magnetization $`m_l(x,y,z)`$ at site $`(xyz)`$. $`m_l(x,y,z)`$ may be defined by the correlation function

$$m_l(x,y,z)=\sqrt{<S_{xyz}S_{x^{}y^{}z^{}}>}$$
(3)   
where $`(xyz)`$ and $`(x^{}y^{}z^{})`$ are topologically equivalent sites with maximal separation distance; brackets denote the thermal average. In the thermodynamic limit, $`L\mathrm{}`$, one recovers the standard definition of the local magnetization $`m(x,y,z)=<S_{xyz}>`$. $`m_l(x,y,z)`$ approaches closely $`m(x,y,z)`$ provided the separation distance between the two equivalent spins is large compared to the correlation length. Certainly, finite–size effects are most severe near criticality, as usual. The deviation of $`m_l`$ from $`m`$ may be monitored by varying the size of the cubes, $`L`$, and by considering the correlation function between spins on equivalent sites with different separation distances (for instance, two corner spins may be connected either by an edge, by a surface diagonal, or by the bulk diagonal).

In Fig. 1 the intriguing profile of the local magnetization at the surface, $`m_l(x,y,1)`$, of a $`40^3`$ Ising cube with equal surface couplings, case (i), is depicted, at $`k_BT/J_b=4.9`$, i.e. $`T0.985T_s`$. The non–monotonic behavior along pathes from the edges or corners towards the center of the surface reflects the influence of bulk spins, as has been discussed before . Crossover to monotonicity of the profile, with the largest magnetization at the corners, is expected to occur even closer to $`T_s`$. At lower temperatures, roughly $`T<T_c`$, the profile is monotonic as well, with the smallest magnetization at the corners due to the different coordination numbers at corners, edges, and surfaces.

Near the surface transition, $`T_s`$, the corner magnetization, say, $`m_3=m_l(1,1,1)`$, is expected to vanish, in the thermodynamic limit, as $`m_3t^{\beta _3}`$, where $`t`$ is the reduced temperature $`t=|TT_s|/T_s`$. To estimate $`\beta _3`$, we consider the effective exponent  $`\beta _{eff}(t)=d\mathrm{ln}m_3/d\mathrm{ln}t`$. When analysing the Monte Carlo data, the derivative is replaced by a difference at discrete temperatures. As $`t0`$, $`\beta _{eff}`$ approaches $`\beta _3`$, provided finite–size effects can be neglected.

The temperature dependence of the effective exponent $`\beta _{eff}`$ for the three different sets of couplings, (i), (ii), and (iii), is shown in Fig. 2, displaying only data which were checked to be unaffected by finite–size effects. Error bars stem from the ensemble averaging performed to determine $`m_3`$. The resulting estimates for the asymptotic critical exponent $`\beta _3`$ are (i) $`0.06\pm 0.01`$ at $`J_e=J_{es}=J_s=2J_b`$, (ii) $`0.14\pm 0.015`$ at $`J_{es}=J_s=2J_b`$ and $`J_e=J_b`$, and (iii) $`0.26\pm 0.02`$ at $`J_e=J_s=2J_b`$ and $`J_{es}=J_b`$. In addition, we estimated $`\beta _3`$ at the ordinary transition, $`J_e=J_{es}=J_s=J_b`$ to be $`\beta _3=1.77\pm 0.05`$, confirming and refining our previous estimate based on computing the corner magnetization from metastable states .– Error bars are inferred from ”reasonable” extrapolations of the effective exponent, see Fig. 2.

To explain the Monte Carlo findings on $`\beta _3`$, note that the critical fluctuations at the surface transition are essentially two–dimensional and that corners are intersection points of the edges. Now, as had been shown before , at the surface transition edges act as ladder– or chain–type defect lines . The critical exponent $`\beta _2`$ of the edge magnetization is non–universal (being non–trivial even in case (i) of equal surface couplings, due to the coupling to bulk spins), varying with the edge, $`J_e`$, and edge–surface, $`J_{es}`$, couplings. To a given set of interactions $`J_e`$ and $`J_{es}`$, one may assign roughly an effective defect coupling of ladder– or chain–type, $`J_d^{eff}`$, yielding the same critical exponent for the defect magnetization in the two–dimensional Ising model, $`\beta _l`$, and for the edge magnetization at the surface transition of the three–dimensional Ising model, $`\beta _2`$. Specificly, for a ladder–type defect, the critical exponent of the magnetization in the ladder rows, $`\beta _l`$, is given by 

$$\beta _l=2\mathrm{arctan}^2(\kappa _l^1)/\pi ^2$$
(4)   
with $`\kappa _l=\mathrm{tanh}(J_l/(k_BT_{2d}))/\mathrm{tanh}(J/(k_BT_{2d}))`$, where $`T_{2d}`$ is the transition temperature. Comparing $`\beta _2`$ and $`\beta _l`$, one may interpret the defect coupling $`J_l`$ of the two–dimensional model as the desired effective coupling $`J_d^{eff}`$ ($`J`$ is the coupling constant away from the defect line, corresponding to $`J_s`$ in the three–dimensional systems).

Following this analogy, the critical exponent of the corner magnetization, $`\beta _3`$, can be related to that of the magnetization at the intersection of three defect lines in the two–dimensional Ising model, $`\beta _i`$, with effective defect couplings, $`J_d^{eff}`$. Indeed, in the two–dimensional Ising model, the value of $`\beta _i`$ has been calculated exactly for three intersecting ladder defects by Henkel et al. , showing a non–universal behavior, with $`\beta _i`$ depending on the strength of the defect couplings, $`J_l`$. If those couplings are weaker than in the rest of the system, then $`\beta _i`$ will increase with decreasing $`J_l(<J)`$, $`\beta _i>1/8`$, 1/8 being the well–known Onsager value in the isotropic two–dimensional Ising model. In turn, if the defect couplings get stronger, then $`\beta _i`$ will get smaller. The concrete expression for $`\beta _i`$ is quite lengthy  and will not be reproduced here, but it can be evaluated in a straightforward way.

The effective ladder-type defect couplings $`J_d^{eff}`$ in the three cases we considered are (i) $`J_d^{eff}1.22J_s`$ corresponding to $`\beta _20.095`$  in the case of equal surface couplings, i.e. an effective enhancement of the couplings at the edges due to the influence of bulk spins, (ii) $`J_d^{eff}0.99J_s`$ corresponding to $`\beta _20.127`$  for weakened edge couplings, i.e. the enhancement is now approximately compensated by the weakening of $`J_e`$, and (iii) $`J_d^{eff}0.74J_s`$ corresponding to $`\beta _20.176`$  for weakened edge–surface couplings, overcompensating the enhancement by the reduction in $`J_{es}`$ (note that the values of $`\beta _2`$ differ significantly from those of $`\beta _3`$). Using these estimates of $`J_d^{eff}`$, one obtains from the exact expression  for the two–dimensional Ising model with three intersecting ladder defects of those strengths the following values for $`\beta _i`$ (i) 0.082 , (ii) 0.128, and (iii) 0.21, in satisfactory agreement with the Monte Carlo findings on $`\beta _3`$. Of course, a more refined analysis had to take into account, e.g., the rather complicated (see also the non–monotonic profile in Fig. 1) nature of the edge as a simultaneously ladder– and chain–type defect line as well as the effect of the bulk spin next to the corner on the corner magnetization. Indeed, the good agreement between $`\beta _3`$ and $`\beta _i`$ in case (ii) may be related to the fact that the chain–like character is rather weak in that situation. The bulk spin is expected to strengthen the effective coupling at the corner especially in case (i), giving rise to the reduction in $`\beta _3`$ as compared to $`\beta _i`$.

Certainly, bulk properties will become critical only at the extraordinary transition, at $`k_BT_c/J_b4.5115`$. For instance, the specific heat $`C`$ is expected to diverge there, in the thermodynamic limit. For finite, $`L^3`$ Ising cubes, one observes that a maximum in $`C`$ near $`T_c`$ shows up only for systems with at least a few thousands spins, getting more pronounced as the system size increases (we studied case (i) with equal surface couplings and $`J_s=2J_b`$). On the other hand, the maximum in $`C`$ near the surface transition, $`T_s`$, dominates for small cubes, becoming more and more suppressed as one increases the size, $`L`$. For cubes of moderate size, say $`15<L<60`$, the temperature dependence of the specific heat is characterised by an easily detectable two–peak structure, with maxima close to $`T_c`$ and $`T_s`$.-The height of the two peaks may be easily varied by replacing the Ising cubes by slabs.

In summary, the corner magnetization at the surface transition of Ising cubes has been found to display non-universal critical behavior, with the critical exponent $`\beta _3`$ of the corner magnetization (being distinct from the corresponding edge exponent $`\beta _2`$) depending on the strength of the edge and edge–surface couplings. The concrete value of $`\beta _3`$ may be approximated rather well from the exactly known value of the critical exponent of the magnetization at the intersection point of three defect lines in the two–dimensional Ising model by estimating effective defect couplings from the edge critical behavior.

###### Acknowledgements.

It is a pleasure to thank M. Henkel and I. Peschel for very helpful suggestions and discussions.