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The simulated annealing algorithm takes random walks through the problem space, looking for points with low energies; in these random walks, the probability of taking a step is determined by the Boltzmann distribution,
p = e^{-(E_{i+1} - E_i)/(kT)}
if E_{i+1} > E_i, and p = 1 when E_{i+1} <= E_i.
In other words, a step will occur if the new energy is lower. If the new energy is higher, the transition can still occur, and its likelihood is proportional to the temperature T and inversely proportional to the energy difference E_{i+1} - E_i.
The temperature T is initially set to a high value, and a random walk is carried out at that temperature. Then the temperature is lowered very slightly according to a cooling schedule, for example: T -> T/mu_T where \mu_T is slightly greater than 1.
The slight probability of taking a step that gives higher energy is what allows simulated annealing to frequently get out of local minima.