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Introducing an energy level between E1 and E2 would create a new energy state for electrons to occupy. This would change the relative energies of E1 and E2, making the transition from E1 to the new level more favorable, and the transition from E1 to E2 less favorable. Since the Boltzmann distribution describes the relative populations of energy levels based on their energy difference, the population of E2 would decrease, and the population of the new level would increase. The precise effect on the population of E2 would depend on the energy difference between E1 and the new level, and between the new level and E2.