This paper reports polarization-resolved temperature-dependent Raman scatte
ring measurements on single crystals of the orthorhombic perovskite colossa
l-magnetoresistive material La1-xCaxMnO3, with x = 0.1, 0.275, 0.3. It is d
emonstrated that two of the Raman Lines undergo an anomalous softening as t
emperature is lowered through Tc, related to the development of magnetic or
der below ambient temperature. Also reported is the presence of second-orde
r scattering, as has been previously predicted for the manganites, Only the
broad features at 500 and 650 cm(-1) that arise from disorder-induced scat
tering contribute to the second-order signal.