Dazhi Liu

Observation of the density minimum in deeply supercooled confined water

Small angle neutron scattering (SANS) is used to measure the density of heavy water contained in 1D cylindrical pores of mesoporous silica material MCM-41-S-15, with pores of diameter of 15 ± 1 Å. In these pores the homogenous nucleation process of bulk water at 235 K does not occur, and the liquid can be supercooled down to at least 160 K. The analysis of SANS data allows us to determine the absolute value of the density of D2O as a function of temperature. We observe a density minimum at 210 ± 5 K with a value of 1.041 ± 0.003 g/cm3. We show that the results are consistent with the predictions of molecular dynamics simulations of supercooled bulk water. Here we present an experimental report of the existence of the density minimum in supercooled water, which has not been described previously.

Observation of high-temperature dynamic crossover in protein hydration water and its relation to reversible denaturation of lysozyme

The diffusive dynamics of hydration water in lysozyme is studied by high-resolution incoherent quasielastic neutron scattering spectroscopy and molecular dynamics (MD) simulations in a temperature range of 290 K<T<380 K. The hydration level of the protein powder sample is kept at h=0.35 gram of water per gram of dry protein to provide monolayer of water coverage on the protein surfaces. Two lysozyme samples, the H(2)O hydrated and the D(2)O hydrated, are measured in the experiments. The difference spectra of the two are used to extract the diffusive dynamics of the hydration water. The self-diffusion constant D of the hydration water is obtained from the analyses of the low-Q spectra. The Arrhenius plot of the inverse diffusion constant [i.e., log(1/D) versus 1/T] shows a dynamic crossover from a super-Arrhenius behavior at low temperatures to an Arrhenius behavior at high temperatures bordered at T(D)=345+/-5 K. We also observe a pronounced increase in the migration distance d of the hydration water molecules above T(D). We present evidence from the neutron scattering experiment that this dynamic crossover temperature in the hydration water coincides with that of the reversible denaturation of lysozyme determined by specific heat measurements. We further performed MD simulations of hydrated lysozyme powder to offer a plausible reason for this coincidence of the crossover phenomenon with the reversible denaturation of the protein.

Density Measurement of 1-D Confined Water by Small Angle Neutron Scattering Method : Pore Size and Hydration Level Dependences

Small angle neutron scattering (SANS) is used to measure the absolute density of water contained in 1-D cylindrical pores of a silica material MCM-41-S with pore diameters of 19 and 15 A. By being able to suppress the homogeneous nucleation process inside the narrow pore, one can keep water in the liquid state down to at least 160 K. From a combined analysis of SANS data from both H(2)O and D(2)O hydrated samples, we determined the absolute value of the density of 1-D confined water. We found that the average density of water inside the fully hydrated 19 A pore is 8% higher than that of the bulk water at room temperature. The temperature derivative of the density shows a pronounced peak at T(L) = 235 K signaling the crossing of the Widom line at ambient pressure and confirming the existence of a liquid-liquid phase transition at an elevated pressure. Pore size and hydration level dependences of the density are also studied.

Scalable numerical approach for the steady-state ab initio laser theory

We present an efficient and flexible method for solving the non-linear lasing equations of the steady-state ab initio laser theory. Our strategy is to solve the underlying system of partial differential equations directly, without the need of setting up a parametrized basis of constant flux states. We validate this approach in one-dimensional as well as in cylindrical systems, and demonstrate its scalability to full-vector three-dimensional calculations in photonic-crystal slabs. Our method paves the way for efficient and accurate simulations of microlasers which were previously inaccessible.

Absence of the Density Minimum of Supercooled Water in Hydrophobic Confinement

The surface effect on the peculiar dynamic and thermodynamic properties of supercooled water, such as the density, has been puzzling the scientific community for years. Recently, using the small angle neutron scattering method, we were able to measure the density of H(2)O confined in the hydrophobic mesoporous material CMK-1-14 from room temperature down to the deeply supercooled temperature 130 K at ambient pressure. We found that the well-known density maximum of water is shifted 17 K lower and, more interestingly, that the previously observed density minimum in hydrophilic confinement disappears. Furthermore, the deduced thermal expansion coefficient shows a much broader peak spanning from 240 to 180 K in comparison with the sharp peak at 230 K in hydrophilic confinement. These present results may help in the understanding of the effect of hydrophobic/hydrophilic interfaces on the properties of supercooled confined water.

Dynamic Crossover Phenomenon in Confined Supercooled Water and Its Relation to the Existence of a Liquid‐Liquid Critical Point in Water

We have observed a Fragile‐to‐Strong Dynamic Crossover (FSC) phenomenon of the α‐relaxation time and self‐diffusion constant in confined supercooled water. The α‐relaxation time is measured by Quasielastic Neutron Scattering (QENS) experiments and the self‐diffusion constant by Nuclear Magnetic Resonance (NMR) experiments. Water is confined in 1‐d geometry in cylindrical pores of nanoscale silica materials, MCM‐41‐S and in Double‐Wall Carbon Nanotubes (DWNT). The crossover phenomenon can also be observed from appearance of a Boson peak in Incoherent Inelastic Neutron Scattering experiments. We observe a pronounced violation of the Stokes‐Einstein Relation at and below the crossover temperature at ambient pressure. Upon applying pressure to the confined water, the crossover temperature is shown to track closely the Widom line emanating from the existence of a liquid‐liquid critical point in an unattainable deeply supercooled state of bulk water. Relation of the dynamic crossover phenomenon to the existence of a density minimum in supercooled confined water is discussed. Finally, we discuss a role of the FSC of the hydration water in a biopolymer that controls the biofunctionality of the biopolymer.We have observed a Fragile‐to‐Strong Dynamic Crossover (FSC) phenomenon of the α‐relaxation time and self‐diffusion constant in confined supercooled water. The α‐relaxation time is measured by Quasielastic Neutron Scattering (QENS) experiments and the self‐diffusion constant by Nuclear Magnetic Resonance (NMR) experiments. Water is confined in 1‐d geometry in cylindrical pores of nanoscale silica materials, MCM‐41‐S and in Double‐Wall Carbon Nanotubes (DWNT). The crossover phenomenon can also be observed from appearance of a Boson peak in Incoherent Inelastic Neutron Scattering experiments. We observe a pronounced violation of the Stokes‐Einstein Relation at and below the crossover temperature at ambient pressure. Upon applying pressure to the confined water, the crossover temperature is shown to track closely the Widom line emanating from the existence of a liquid‐liquid critical point in an unattainable deeply supercooled state of bulk water. Relation of the dynamic crossover phenomenon to the existence...

Interaction-induced mode switching and threshold condensation in steady-state microlasers

In this talk we discuss two novel effects in steady state microlasers. The first one is interaction-induced mode switching (IMS), where the onset of a new lasing mode switches off an existing mode via a negative power slope. Its a deterministic effect in steady state lasing and caused by cross saturation of the gain medium, hence its different from dynamic mode switching or hopping. For a fixed pump profile, a simple analytic criterion for the occurrence of IMS is given in terms of their self- and cross-interaction coefficients and non-interacting thresholds, which is verified for the example of a two-dimensional microdisk laser. When the spatial pump profile is varied as the pump power is increased, IMS can be induced even when it would not occur with a fixed pump profile, as we show for two coupled laser cavities.

Microcavity laser linewidth theory

We present a multimode laser-linewidth formula that generalizes previous theories, including corrections for cavity losses, nonlinear gain and dispersion, but is derived in a more general setting and is therefore applicable to complex wavelength-scale lasers.