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Why is it that energy is released from electrons when they move from one atom to a more electronegative one?

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The previous answer is correct. I just wanted to add that atoms, electrons and generally matter, tries to ''organise'' itself in order to adopt a state, where it would have the lowest energy possible. An electronegative atom tends to attract electrons and has the ability of handling their charge better. Thus when an electron moves from a less electronegative atom to a more electronegative one, it is like moving from a state of high energy to a state of low energy. This is also described as realease of energy.

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Due to difference in electronegativities the atoms have different binding energies and this difference is radiated in some form. If you're talking about a transition in a single atom the difference is the binding energies of different orbital/orbits/sheels.

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