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To answer your question briefly, when electricity (ie electrons) pass through neon they 'excite' (give energy too) other electrons. Unfortunately Electrons can only have certain discrete energy levels in an atom, if they are excited they will momentarily increase their energy and occupy an unallowed energy level in the atom, this means they are unstable and so to get back to their previous energy level they must let a little bit of their energy go. They let this go by releasing Electromagnetic radiation (this is what light is part of), and dependant on how much of energy is released determines what colour light you will see. Fortunately when the electrons in neon get excited they release EM radiation with the right level of energy for our eyes to interpret it as red light.

I hope this answers your question satisfactorily, if you want it in any more detail then please ask.

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