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A cooling schedule for simulated annealing specifies successive effective temperatures and how many proposals to attempt at each. For example, $T_k=T_0{r}^k$ with $0<r<1$, using the geometric sequence, can define stages of equal chosen length. Changing $T$ changes the transition matrix: if the state probability distribution is ${\mu }_n$, then ${\mu }_{n+1}={\mu }_n{P}_{T_n}$, which generally differs from ${\pi }_{T_{n+1}}$. Time spent at one temperature must be compared with its mixing time before equilibrium intuition is justified.

In the five-state barrier example for simulated annealing, fixed $T_{\ast }>0$ gives a finite irreducible Markov chain, so $4$ is eventually visited with probability one. That unbounded-time statement gives no fixed finite deadline. Over any finite number $N$ of trials starting at $1$, the probability of staying at $1$ throughout isEach factor is the rejection probability at $1$. This is an explicit failure event even when every $T_n$ is positive: the best visited objective function value remains $1$, above the global minimum value $0$. More exploratory proposals can help cross a barrier; cooling before those moves occur can preserve a poor local minimum. Successful asymptotic schedules need additional analysis of the allowed moves and barriers.

Historically, Scott Kirkpatrick, Charles Daniel Gelatt Jr. and Mario P. Vecchi connected statistical mechanics with mathematical optimization in 1983. They adapted the Metropolis–Hastings algorithm to cooling searches with symmetric proposals and illustrated computer-design problems.^[ref]

On a finite state space $F$ with finite objective function values, the fixed-$T$ target is a Boltzmann distribution:The partition function $Z_T$ normalizes the weights but cancels from the Metropolis–Hastings acceptance probability. A short detailed balance proof explains the target. With symmetric $q$ and $x\ne y$,Summing over $x$ gives ${\pi }_T{P}_T={\pi }_T$, so this is a stationary distribution. On a finite state space, a connected graph of positive symmetric proposals makes the accepted Markov chain an irreducible Markov chain. Convergence from any starting state additionally requires an aperiodic Markov chain; one positive self-transition suffices under irreducibility. Replacing $q$ by $(I+q)/2$ ensures this. For asymmetric $q$, require connectivity through bidirectional proposals: one-way proposals are rejected.^[ref]

In the five-state barrier example for simulated annealing, $T_{\ast }=1/\ln 2$ gives exact Boltzmann weights $2^{-E(x)}$. Multiplying by $16$ givesFor the uphill edge, detailed balance is visible numerically:Thus the global minimum has the largest individual stationary probability, $16/33$, but is far from certain at this positive $T_{\ast }$. At $T_{\ast }/2$ the exact stationary distribution is $(16,64,1,16,256)/353$.

For any finite $F$, let $M$ be the set of global minima and $E_{\min }$ the smallest objective function value. Cancelling $e^{-E_{\min }/T}$ from numerator and denominator shows that each nonminimal state's weight tends to zero as $T\downarrow 0$, while every state in $M$ has equal weight. Therefore ${\pi }_T$ tends to the uniform distribution on $M$. This is a statement about a family of equilibrium probability distributions; it does not prove that a cooling Markov chain follows that family.