The supercooled liquid silicon, modeled by Stillinger-Weber potential, shows anomalous increase in heat capacity $C_p$, with a maximum $C_p$ value close to 1060 K at zero pressure. We study equilibration and relaxation of the supercooled SW Si, in th
e temperature range of 1060 K--1070 K at zero pressure. We find that as the relaxation of the metastable supercooled liquid phase initiates, a straight line region (SLR) is formed in cumulative potential energy distributions. The configurational temperature corresponding to the SLR is close to 1060 K, which was earlier identified as the freezing temperature of 4-coordinated amorphous network. The SLR is found to be tangential to the distribution of the metastable liquid phase and thus influences the broadness of the distribution. As the bath temperature is reduced from 1070 K to 1060 K, the effective temperature approaches the bath temperature which results in broadening of the metastable phase distribution. This, in turn, causes an increase in overall fluctuations of potential energy and hence an increase of heat capacity. We also find that during initial stages of relaxation, 4-coordinated atoms form 6-membered rings with a chair--like structure and other structural units that indicate crystallization. Simultaneously a strong correlation is established between the number of chair-shaped 6-membered rings and the number of 4-coordinated atoms in the system. This shows that all properties related to 4-coordinated particles are highly correlated as the SLR is formed in potential energy distributions and this can be interpreted as a consequence of `freezing of amorphous network formed by 4-coordinated particles.
