Browsing by Author "Rafique, M."

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Open Access
Mechanical deformation affects the counterion condensation in highly swollen polyelectrolyte hydrogels
(Royal Society of Chemistry, 2023-09-15) Rafique, M.; Erbaş, Aykut
Polyelectrolyte gels can generate electric potentials under mechanical deformation. While the underlying mechanism of such a response is often attributed to changes in counterion-condensation levels or alterations in the ionic conditions in the pervaded volume of the hydrogel, the exact molecular origins are largely unknown. By using all-atom molecular dynamics simulations of a polyacrylic acid hydrogel in explicit water as a model system, we simulate the uniaxial compression and uniaxial stretching of weakly to highly swollen (i.e., between 60–90% solvent content) hydrogel networks and calculate the microscopic condensation levels of counterions around the hydrogel chains. The counterion condensation under deformation is highly non-monotonic. Ionic condensation around the constituting chains of the deformed hydrogel tends to increase as the chains are stretched. This increase reaches a maximum and decreases as the chains are strongly stretched. The condensation around the collapsed chains of the hydrogel is weakly affected by the deformation. As a result, both compressing and stretching the model hydrogel lead to an overall increase in the counterion condensation. The effect vanishes for weakly swollen hydrogels, for which most ions are already condensed. The simulations with single, stretched polyelectrolyte chains show a qualitatively similar response, suggesting the effect of chain elongation on the ionic distribution throughout the hydrogel. Notably, this deformation-induced counterion condensation phenomenon does not occur in a polyelectrolyte solution at its critical concentration, indicating the role of hydrogel topology constraining the chain ends. Our results indicate that counterion condensation in a deforming polyelectrolyte hydrogel can be highly heterogeneous and exhibit a rich behaviour of electrostatic responses.
Open Access
Ultra-narrow linewidth photo-emitters in polymorphic selenium nanoflakes
(Wiley, 2022-07-12) Hussain, N.; Ahmed, S.; Tepe, H. U.; Huang, K.; Avishan, N.; He, S.; Rafique, M.; Farooq, U.; Kasirga, Talip Serkan; Bek, A.; Turan, R.; Shehzad, K.
Photoluminescence (PL) in state-of-the-art 2D materials suffers from narrow spectral coverage, relatively broad linewidths, and poor room-temperature (RT) functionality. The authors report ultra-narrow linewidth photo-emitters (ULPs) across the visible to near-infrared wavelength at RT in polymorphic selenium nanoflakes (SeNFs), synthesized via a hot-pressing strategy. Photo-emitters in NIR exhibit full width at half maximum (Γ) of 330 ± 90 µeV, an order of magnitude narrower than the reported ULPs in 2D materials at 300 K, and decrease to 82 ± 70 µeV at 100 K, with coherence time (τc) of 21.3 ps. The capping substrate enforced spatial confinement during thermal expansion at 250 °C is believed to trigger a localized crystal symmetry breaking in SeNFs, causing a polymorphic transition from the semiconducting trigonal (t) to quasi-metallic orthorhombic (orth) phase. Fine structure splitting in orth-Se causes degeneracy in defect-associated bright excitons, resulting in ultra-sharp emission. Combined theoretical and experimental findings, an optimal biaxial compressive strain of −0.45% cm−1 in t-Se is uncovered, induced by the coefficient of thermal expansion mismatch at the selenium/sapphire interface, resulting in bandgap widening from 1.74 to 2.23 ± 0.1 eV. This report underpins the underlying correlation between crystal symmetry breaking induced polymorphism and RT ULPs in SeNFs, and their phase change characteristics. © 2022 Wiley-VCH GmbH.