Transient pump-probe reflectance measurements on La_{0.67}Ca_{0.33}MnO_3/MgO and La_{0.67} Ca_{0.33}MnO_3/SrTiO_3 thin films reveal a hitherto unknown magnetization-dependent energy gap that determines the relaxation process of the optically excited charge carriers on the picosecond time scale. In the case of La_{0.67}Ca_{0.33}MnO_3/SrTiO_3, the subsequent reflectance dynamics at low temperatures is determined to be substrate-induced strain that drives the sample into a metastable state characterized by an increased number of paramagnetic domains.
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