Comment on "Solvent-Induced Negative Energetic Elasticity in a Lattice Polymer Chain''

Abstract

In a recent Letter, Shirai and Sakumichi [Phys. Rev. Lett. 130, 148101 (2023), arXiv:2202.12483] presented a study focusing on the origin of a temperature-dependent negative contribution $G_U(T)$ to the elastic modulus $G(T)$ of hydrogels [Yoshikawa et al., Phys. Rev. X 11, 011045 (2021)]. The authors support their findings through an energy-related stiffness $k_U(r,T)$ obtained from a single chain, with $r$ being the end-to-end distance of a random walk on a 3D lattice. It is argued that the parameter $\varepsilon$ related to polymer-solvent interactions is positive, so the energy $E_s$ of an elongated state should be smaller than the energy $E_b$ of a more compact state. We believe that the analogy between $G_U(T)$ and $k_U(r,T)$ might have misled their claim that $G_U(T)<0$ when $\varepsilon>0$.