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Is it not possible that during transition of an electron from higher to lower energy state, it can release multiple photons of low energy instead of a single photon of the exact energy difference between the two states?

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Yes it's possible, and it's called (unsurprisingly) two photon emission.

However the probability of two or multi photon emission is generally lower than for single photon emission by several orders of magnitude, so it's hard to observe.

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