"usually, the capital city is the largest city"

This is because of the corruption of politics. Politicians leech the wealth of a nation and bring it to the capital city like vampires. We should instead look to build countries where the capital city is an insignificant backwater.

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Once the politicians start leeching, network effects often bring more legitimate wealth to the capital city alongside it. But yes, the main reason it's specifically the capital is kings or politicians.

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