We consider certain self-adjoint observables for the KMS state associated to the Hamiltonian $H= σ^x \otimes σ^x$ over the quantum spin lattice $\mathbb{C}^2 \otimes \mathbb{C}^2 \otimes \mathbb{C}^2 \otimes ...$. For a fixed observable of the form $L \otimes L \otimes L \otimes ...$, where $L:\mathbb{C}^2 \to \mathbb{C}^2 $, and for the zero temperature limit one can get a naturally defined stationary probability $μ$ on the Bernoulli space $\{1,2\}^\mathbb{N}$. This probability is ergodic but it is not mixing for the shift map. It is not a Gibbs state for a continuous normalized potential but its Jacobian assume only two values almost everywhere. Anyway, for such probability $μ$ we can show that a Large Deviation Principle is true for a certain class of functions. The result is derived by showing the explicit form of the free energy which is differentiable.