From thermodynamic analysis we demonstrate that during metal-insulator transitions in pure matters, a nonequilibrium homogeneous state may be unstable against charge density modulations with certain wavelengths, and thus evolves to the equilibrium phase through transient electronic phase separation. This phase instability occurs as two inequalities between the first and the second derivatives of the free energy with respect to the order parameter are fulfilled. The dominant wavelength of the modulated phase is also derived. The computer simulation further confirms the theoretical derivation. Employing the pre-established phase-field model of VO$_2$, we show that this transient electronic phase separation may take place in VO$_2$ upon photoexcitation.
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