Due to their sub picosecond temporal resolution, coherent Raman spectroscopies have been proposed as a viable extension of Spontaneous Raman (SR) thermometry, to determine dynamics of mode specific vibrational energy content during out of equilibrium molecular processes. Here we show that the presence of multiple laser fields stimulating the vibrational coherences introduces additional quantum pathways, resulting in destructive interference. This ultimately reduces the thermal sensitivity of single spectral lines, nullifying it for harmonic vibrations and temperature independent polarizability. We demonstrate how harnessing anharmonic signatures such as vibrational hot bands enables coherent Raman thermometry.
