As listed in Table and Table , the simulation outcomes agree with the measured phonon frequency shifts. The relaxation of the bond length and energy in terms of vibration frequency that features the stiffness of an oscillating dimer in responding to a load of perturbation. One can readily correlate the frequency shift (Δω) to the relaxation of bond length (d) through the equation of frequency shift (we have described it in the section of Method), which suggests that if a phonon peak undergoes redshift, its vibrating bond will expand and both the bond energy (E) and the bond length relax in opposite directions. Specifically, the THF hydration shortens the H-O bond by -2.04 % and lengthens the H:O by 6.04%. DMSO hydration displays a similar bond length variation, showing -1.64% and 3.74% strain for the H-O and the H:O, respectively. Regarding to the intra-solute bonds, the C-O of THF and S=O bonds of DMSO become longer indeed compared with those in the pure organic molecules. The O:H strain for the O:H-C is much greater than that for the O:H-O (6.04% vs.65.23% for THF and 3.74% vs.44.69% for DMSO) due to the hydrophobicity effect of the methyl functionaries. The C-S contract -0.38% compared to those in its parent DMSO. These findings would enrich the connotation of hydration interfacial bonding profoundly by incorporating the coupling, charge inversion, and coupling-enabled cooperativity and polarizability upon perturbation, which should offer alternative impacts on dealing with systems involving molecular interactions, such as cryoprotectants, electrolytes, etc.