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Sum frequency generation (SFG) necessitates both noncentrosymmetry and coherence over multiple length scales. These requirements make vibrational SFG spectroscopy capable of probing structural information of noncentrosymmetric organic crystals interspersed in polymeric matrices and their three-dimensional spatial distributions within the matrices without spectral interferences from the amorphous components. However, this analysis is not as straightforward as simple vibrational spectroscopy or scattering experiments; it requires knowing the molecular hyperpolarizability of SFG-active vibrational modes and their interplay within the coherence length. This study demonstrates how density function theory (DFT) calculations can be used to construct the molecular hyperpolarizability of a model system and combine it with the SFG theory to predict the polarization and azimuth angle dependences of SFG intensities. A model system with short peptide chains mimicking β-sheet domains in Bombyx mori silk was chosen. SFG signals of the amide-I, II, III, and A bands and one of the CH deformation modes were simulated and compared with the experimental results and the predictions from the group theory. The SFG features of amide-I and A bands of antiparallel β-sheet could be explained with DFT-based theoretical calculations. Although vibrational coupling with neighboring groups breaks the symmetry of the D2 point group, the group theory approach and DFT calculations gave similar results for the amide-I mode. The DFT calculation results for amide-II did not match with experimental data, which suggested vibrational coupling within a larger crystalline domain may dominate the SFG spectral features of these modes. This methodology can be applied to the structural analysis of other biopolymers. 

A key component of cooling devices is the transfer of entropy from the cold load to heat sink. An electrocaloric (EC) polymer capable of generating both large electrocaloric effect (ECE) and substantial electroactuation can enable EC cooling devices to pump heat without external mechanisms, resulting in compact designs and enhanced efficiency. However, achieving both high ECE and significant electroactuation remains challenging. Herein, it is demonstrated that poly(vinylidene fluoride‐trifluoroethylene‐chlorofluoroethylene‐double bond) [P(VDF‐TrFE‐CFE‐DB)] tetrapolymers can simultaneously generate high electrocaloric effects and electroactuations under low fields. These P(VDF‐TrFE‐CFE‐DB) tetrapolymers are synthesized through the dehydrochlorination of P(VDF‐TrFE‐CFE) terpolymer. By facile tuning the composition of the initial terpolymer to avoid pure relaxor state, tetrapolymers with optimal DB compositions are achieved, near the critical endpoint of normal ferroelectric phase with diffused phase transition. The nearly vanishing energy barriers between the nonpolar to polar phases result in a strong electrocaloric response and significant electroactuation. Specifically, the P(VDF‐TrFE‐CFE‐DB) tetrapolymer exhibits an EC entropy change ΔSof 100 J kg⁻¹ K⁻¹under 100 MV m⁻¹: comparable to state‐of‐the‐art (SOA) EC polymers, while delivering nearly twice the electroactuation of the SOA EC polymers. This work presents a general strategy for developing EC materials that combine large electrocaloric effect and electroactuation at low electric fields. 

The molecules with higher tribochemical reactivity exhibited smaller activation volume, implying that less mechanical energy was required to initiate tribochemical reactions. 

Abstract Mechanical stress can directly activate chemical reactions by reducing the reaction energy barrier. A possible mechanism of such mechanochemical activation is structural deformation of the reactant species. However, the effect of deformation on the reaction energetics is unclear, especially, for shear stress-driven reactions. Here, we investigated shear stress-driven oligomerization reactions of cyclohexene on silica using a combination of reactive molecular dynamics simulations and ball-on-flat tribometer experiments. Both simulations and experiments captured an exponential increase in reaction yield with shear stress. Elemental analysis of ball-on-flat reaction products revealed the presence of oxygen in the polymers, a trend corroborated by the simulations, highlighting the critical role of surface oxygen atoms in oligomerization reactions. Structural analysis of the reacting molecules in simulations indicated the reactants were deformed just before a reaction occurred. Quantitative evidence of shear-induced deformation was established by comparing bond lengths in cyclohexene molecules in equilibrium and prior to reactions. Nudged elastic band calculations showed that the deformation had a small effect on the transition state energy but notably increased the reactant state energy, ultimately leading to a reduction in the energy barrier. Finally, a quantitative relationship was developed between molecular deformation and energy barrier reduction by mechanical stress.