# Comment on ‘Ising Pyrochlore Magnets: Low Temperature Properties, “Ice Rules,” and Beyond’ by R. Siddharthan et al.

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Siddharthan et al.  discuss the competition between dipolar coupling and superexchange in pyrochlore magnets with $`111`$ Ising-like anisotropy, such as Ho<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub>  and Dy<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> . In the simplest approximation for Ho<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub>, with Ising spins and nearest-neighbor ferromagnetic exchange, one obtains the “spin ice” model that predicts a macroscopically degenerate ground state . Consistent with this, $`\mu `$SR and neutron scattering data  find no phase transition in Ho<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> in zero field down to at least 50 mK, and at that temperature the neutron scattering pattern is consistent with the spin ice ground state . On the other hand, the dipolar coupling, $`J_D`$, in these materials, is of the same order of magnitude as superexchange, $`J_S`$. Siddharthan et al. derive an estimate for $`J_S=1.92`$ K for the near neighbour exchange and $`J_D=2.35`$ K. These values are consistent with our own estimates $`J_D=2.35`$K, and $`J_S=1.4\pm 0.5`$ K from single crystal measurements where demagnetizing effects were explicitly accounted for, and which correspond to the Curie-Weiss temperature of +1.9 K, quoted in Ref. . Using their estimated value of $`J_S`$, Siddharthan et al. simulated a model in which the dipolar summation is truncated at five nearest neighbours, and find a transition to a partially ordered phase marked by a sharp peak in the heat capacity, $`C(T)`$, at $`T0.8`$. They further argue that such a picture applies to Ho<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> by commenting that the experimental heat capacity shows, as their simulation does, a steep increase at about 1 K and that the experimental data for Ho<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> suggest a vanishing entropy for the ground state (on integrating $`C(T)/T`$). Their conclusion of a phase transition in Ho<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> is inconsistent with the experimental $`\mu `$SR and neutron data of Refs .

In view of the very large hyperfine coupling in Ho, as observed in many other Ho-containing compounds such as HoF<sub>3</sub> , it is necessary to include a component from the nuclear spin, $`I`$. Blöte et al.  find a heat capacity in the pyrochlore Ho<sub>2</sub>GaSbO<sub>7</sub> very similar to the one of Ho<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub>, which they model below 2 K as a simple Schottky anomaly with the theoretical maximum for Ho ($`I=7/2`$) of $`0.9`$ R at a temperature of about 0.3 K.

In this Comment we argue that Ho<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> does in fact exhibit spin ice behavior, and that the experimental specific heat data can be accounted for in terms of a dipolar spin ice model  and by including an expected contibution from the nuclear spins  to the appropriate long-range treatment of the dipole-dipole interactions.

Dipole-dipole interactions are conditionally convergent due to their $`1/r^3`$ nature and their lattice summation must be considered with care . In order to include the long range nature of the dipole-dipole interaction, we have used the standard Ewald method in our Monte Carlo simulations with either of the above set of $`\{J_S,J_D\}`$ values. We found it sufficient to simulate $`4\times 4\times 4`$ cubic cells (1024 spins) with $`10^6`$ Monte Carlo steps per spin.

Figure 1 shows the electronic spin part heat capacity for $`J_s=1`$ K and $`J_D=2.35`$ K (open squares). The total entropy is within 2% of $`R\{\mathrm{ln}(2)(1/2)\mathrm{ln}(3/2)\}`$ and therefore agrees with that of spin ice . We have found in our Ewald simulations that dipolar spin ice occurs for all values $`J_S/J_D>0.91`$, which includes the value of Ref. , and that fully developped $`Q=0`$ long-range antiferromagnetic order occurs for $`J_S/J_D<0.91`$, with no partially frozen or ordered state as found in Ref. . The open circles show the sum of this magnetic heat capacity with a nuclear Schottky anomaly as found in Ho<sub>2</sub>GaSbO<sub>7</sub> . We find that these results reproduce reasonably well the experimental data presented in Ref.  (filled circles), and is definitely more accurate than the model proposed by Siddharthan et al. Equivalently, subtracting the nuclear contribution from the magnetic heat capacity measured in Ref.  leads to a heat capacity similar to that found in the spin ice material Dy<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> . In conclusion, we argue that the experimental specific heat of Ho<sub>2</sub>Ti<sub>2</sub>O<sub>7</sub> can be accounted for by the sum of a dipolar spin ice magnetic contribution and a nuclear hyperfine Shottky anomaly with no need to invoke a transition to a partially ordered state.