Boson peak and medium-range elastic heterogeneity in calcium silicate hydrate probed by terahertz spectroscopy and low-temperature calorimetry
The boson peak (BP), a universal vibrational anomaly of disordered solids, has been predicted but not systematically characterized in calcium silicate hydrate (C-S-H), the binding phase of hardened cement. Building on a preliminary terahertz survey, we characterize the BP across five Ca/Si ratios (0.5-1.7) using terahertz time-domain spectroscopy (THz-TDS) and low-temperature calorimetry, two probes of vibrational dynamics that complement the static picture of conventional structural methods. After Bruggeman correction for crystalline impurities, both probes locate the BP near 1 THz; they agree on frequency but diverge in intensity. The terahertz integrated spectral weight and the calorimetric Cp/T3 peak both fall monotonically with Ca/Si, whereas the apparent terahertz peak height is maximal at Ca/Si = 1.0, where damping is low and oscillator strength still substantial. This decoupling marks a structural crossover between silicate-chain depolymerization and interlayer calcium filling. From the BP we obtain a medium-range dynamical correlation length of order 1 nm (0.3-2 nm) and a coherent-potential elastic-heterogeneity parameter that decreases from gamma = 0.98 to 0.48 as Ca/Si rises; the Debye-normalized BP frequency (nu_BP/nu_D = 0.15-0.17) places C-S-H within the range reported for silicate glasses. Because gamma governs the distribution of energy barriers for local structural rearrangements, it provides a quantitative, composition-resolved descriptor relevant to the intrinsic creep and thermal transport of C-S-H, linking nanoscale vibrational dynamics to the macroscopic durability of concrete. The dual-probe boson-peak approach is transferable to other amorphous solids, including the supplementary cementitious materials of low-carbon cements.