Local and diffusive dynamics of LiCl aqueous solutions in pristine and modified silica nanopores.

We use 1H, 2H, and 7Li nuclear magnetic resonance to investigate local and diffusive dynamics of LiCl-7H2O and LiCl-7D2O solutions in pristine and functionalized silica nanopores in a component-selective manner. Recently, we showed that the solution dynamics become slower when the diameter of the pristine pores is reduced. Here, we determine the effects of (aminopropyl)triethoxysilane and dye surface functionalizations on the motions of the water molecules and lithium ions from ambient temperatures down to the glass transition. The local and diffusive solution dynamics are similar in both functionalized pores but, on average, slower than in pristine pores with comparable diameters. When the exchange between different confinement regions is sufficiently slow at reduced temperatures, bimodal water and lithium dynamics may be observed. We attribute this bimodality to bulk-like motion in the pore centers and slowed-down motion at the pore walls. For the lithium ions, a bimodality observed in the pristine pores is absent in the functionalized ones. We conjecture that the steric hindrance and electrostatic interactions associated with the grafted functional groups interfere with the formation of a defined electric double layer, while the enhanced surface roughness and unequal charge distribution result in overall slower dynamics. Thus, the nature of the walls is an important parameter for the solution dynamics. Thereby, in situ measurements of the pH value inside the silica pores using the grafted dye molecules reveal that observed changes in the pH value in response to the surface functionalization are of limited relevance for the water reorientation.

Competing ultrafast energy relaxation pathways in photoexcited graphene.

For most optoelectronic applications of graphene, a thorough understanding of the processes that govern energy relaxation of photoexcited carriers is essential. The ultrafast energy relaxation in graphene occurs through two competing pathways: carrier-carrier scattering, creating an elevated carrier temperature, and optical phonon emission. At present, it is not clear what determines the dominating relaxation pathway. Here we reach a unifying picture of the ultrafast energy relaxation by investigating the terahertz photoconductivity, while varying the Fermi energy, photon energy and fluence over a wide range. We find that sufficiently low fluence (≲4 µJ/cm(2)) in conjunction with sufficiently high Fermi energy (≳0.1 eV) gives rise to energy relaxation that is dominated by carrier-carrier scattering, which leads to efficient carrier heating. Upon increasing the fluence or decreasing the Fermi energy, the carrier heating efficiency decreases, presumably due to energy relaxation that becomes increasingly dominated by phonon emission. Carrier heating through carrier-carrier scattering accounts for the negative photoconductivity for doped graphene observed at terahertz frequencies. We present a simple model that reproduces the data for a wide range of Fermi levels and excitation energies and allows us to qualitatively assess how the branching ratio between the two distinct relaxation pathways depends on excitation fluence and Fermi energy.