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First, the "head of state" is another name for the president of a country or the prime minister (some countries have a president, some have a prime minister). Barack Obama is America's head of state; David Cameron is currently the head of state in England. "Heads of state" ('state' is always singular, since it is an idiom. and the word 'state' means a country or nation in this expression) refer to more than one president or prime minister.

You cannot make the expression plural-- if you do, you change the meaning. "Heads of states" (actually, "heads of the states") could refer to governors of individual states in the United States, but this is not how we would say it-- we would refer to the "leader" or the "chief executive" of a state, or say "who is the governor of your state?" In the USA, there are 50 states, and each one has a governor. But there is only one president of the United States.

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