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Knowledge of the temperature dependence of the isobaric specific heat (Cp) upon deep supercooling can give insights regarding the anomalous properties of water. If a maximum in Cp exists at a specific temperature, as in the isothermal compressibility, it would further validate the liquid–liquid critical point model that can explain the anomalous increase in thermodynamic response functions. The challenge is that the relevant temperature range falls in the region where ice crystallization becomes rapid, which has previously excluded experiments. Here, we have utilized a methodology of ultrafast calorimetry by determining the temperature jump from femtosecond X-ray pulses after heating with an infrared laser pulse and with a sufficiently long time delay between the pulses to allow measurements at constant pressure. Evaporative cooling of ∼15-µm diameter droplets in vacuum enabled us to reach a temperature down to ∼228 K with a small fraction of the droplets remaining unfrozen. We observed a sharp increase in Cp, from 88 J/mol/K at 244 K to about 218 J/mol/K at 229 K where a maximum is seen. The Cp maximum is at a similar temperature as the maxima of the isothermal compressibility and correlation length. From the Cp measurement, we estimated the excess entropy and self-diffusion coefficient of water and these properties decrease rapidly below 235 K.

Femtosecond optical spectroscopy revealed that the coherent structural dynamics accompanying LIESST was stronger with d–d than MLCT excitation.

Photo-switchable 11 nm nanocrystals of the coordination network Cs{Co[Fe(CN)6]} were obtained using a template-free method. The nanocrystals were recovered from the colloidal solutions as solid materials surrounded by cetyltrimethylammonium (CTA) cations or embedded in the organic polymer polyvinylpyrrolidone (PVP). Complementary magnetic, spectroscopic and structural techniques, including EPR Spectroscopy, reveal a majority (≈70%) of the low spin and photoactive diamagnetic Co III Fe II pairs located in the core of the nanocrystals and a mixture of Co II Fe II and Co II Fe III species present mainly within the shell of the objects. While bulk compounds with similar vacancy concentration do not exhibit noticeable photoinduced charge transfer, the obersved photoactivity of the nanocrystals is ascribed to their nanometric size. The relaxation temperature of the photo-induced state shifts upwards by ≈ 55 K when PVP is replaced by CTA. This is ascribed to the larger rigidity of the dense CsCoFe_CTA material whose metastable state is lower than for CsCoFe_PVP leading to a larger relaxation energy barrier and, therefore, to higher relaxation temperature.

One of the main challenges in ultrafast material science is to trigger phase transitions with short pulses of light. Here we show how strain waves, launched by electronic and structural precursor phenomena, determine a coherent macroscopic transformation pathway for the semiconducting-to-metal transition in bistable Ti3O5 nanocrystals. Employing femtosecond powder X-ray diffraction, we measure the lattice deformation in the phase transition as a function of time. We monitor the early intra-cell distortion around the light absorbing metal dimer and the long range deformations governed by acoustic waves propagating from the laser-exposed Ti3O5 surface. We developed a simplified elastic model demonstrating that picosecond switching in nanocrystals happens concomitantly with the propagating acoustic wavefront, several decades faster than thermal processes governed by heat diffusion.

Abstract:We studied the transient electron-transfer process in CsCoFe and RbMnFe Prussian Blue analogues by time-resolved X-ray absorption near-edge structure (XANES) and by time-resolved optical spectroscopy. We performed time-resolved studies on CsCoFe nanocrystals dispersed in solution. The XANES results obtained at room temperature clearly evidence Co III (low spin)Fe II →Co II (high spin)Fe III electron transfer between the metal centers through opposite spectral shifts at the Fe and Co

Aperiodic composite crystals present long-range order without translational symmetry. These materials may be described as the intersection in three dimensions of a crystal which is periodic in a higher-dimensional space. In such materials, symmetry breaking must be described as structural changes within these crystallographic superspaces. The increase in the number of superspace groups with the increase in the dimension of the superspace allows many more structural solutions. This is illustrated in n-nonadecane-urea, revealing a fifth higher-dimensional phase at low temperature.