Exploring pressure effects on metallic nanoparticles and surrounding media through plasmonic sensing

The sensing capabilities of gold nanorods under high-pressure conditions were investigated in methanol-ethanol mixtures (up to 13 GPa) and in water (up to 9 GPa) through their optical extinction. The longitudinal SPR band of AuNR exhibits a redshift with pressure which is the result of two main competing effects: compression of the conduction electrons which increases the bulk plasma frequency (blueshift) and increase in the solvent density (redshift). The variation in de SPR peak wavelength allows us to estimate the bulk modulus of the gold nanoparticles with a precision of 10 % and to obtain analytical functions providing the pressure dependence of the refractive index of water in three phases: liquid, ice VI and ice VII. Furthermore, the SPR band shows abrupt jumps at the liquid to ice phase VI and ice phase VII transitions, which are in accordance with the first-order character of these transitions.Financial support from Project PGC2018-101464-B-I00 (FEDER) and MALTA-Consolider Team (RED2018-102612-T) of the Ministerio de Ciencia, Innovación y Universidades is acknowledged

Pressure-Induced Phase-Transition Sequence In Cof 2 : An Experimental And First-Principles Study On The Crystal, Vibrational, And Electronic Properties

We report a complete structural study of CoF2 under pressure. Its crystal structure and vibrational and electronic properties have been studied both theoretically and experimentally using first-principles density functional theory (DFT) methods, x-ray diffraction, x-ray absorption at Co K-edge experiments, Raman spectroscopy, and optical absorption in the 0–80 GPa range. We have determined the structural phase-transition sequence in CoF2 and corresponding transition pressures. The results are similar to other transition-metal difluorides such as FeF2 but different to ZnF2 and MgF2, despite that the Co2+ size (ionic radius) is similar to Zn2+ and Mg2+. We found that the complete phase-transition sequence is tetragonal rutile (P42/mnm) → CaCl2 type (orthorhombic Pnnm) → distorted PdF2 (orthorhombic Pbca)+PdF2 (cubic Pa3¯) in coexistence → fluorite (cubic Fm3¯m) → cotunnite (orthorhombic Pnma). It was observed that the structural phase transition to the fluorite at 15 GPa involves a drastic change of coordination from sixfold octahedral to eightfold cubic with important modifications in the vibrational and electronic properties. We show that the stabilization of this high-pressure cubic phase is possible under nonhydrostatic conditions since ideal hydrostaticity would stabilize the distorted-fluorite structure (tetragonal I4/mmm) instead. Although the first rutile → CaCl2-type second-order phase transition is subtle by Raman spectroscopy, it was possible to define it through the broadening of the Eg Raman mode which is split in the CaCl2-type phase. First-principles DFT calculations are in fair agreement with the experimental Raman mode frequencies, thus providing an accurate description for all vibrational modes and elastic properties of CoF2 as a function of pressure

Pressure-and temperature induced phase transitions, piezochromism, NLC behaviour and pressure controlled Jahn–Teller switching in a Cu-based framework

In situ single-crystal diffraction and spectroscopic techniques have been used to study a previously unreported Cu-framework bis[1-(4-pyridyl)butane-1,3-dione]copper(II) (CuPyr-I). CuPyr-I was found to exhibit high-pressure and low-temperature phase transitions, piezochromism, negative linear compressibility, and a pressure induced Jahn?Teller switch, where the switching pressure was hydrostatic media dependent.The support by the Spanish Ministerio de Econom´ıa, Industria y Competitividad (PGC2018-101464-B-I00), and INNVAL 18/28 is also acknowledged

Pressure-induced phase-transition sequence in CoF2: An experimental and first-principles study on the crystal, vibrational, and electronic properties

We report a complete structural study of CoF2 under pressure. Its crystal structure and vibrational and electronic properties have been studied both theoretically and experimentally using first-principles density functional theory (DFT) methods, x-ray diffraction, x-ray absorption at Co K-edge experiments, Raman spectroscopy, and optical absorption in the 0–80 GPa range. We have determined the structural phase-transition sequence in CoF2 and corresponding transition pressures. The results are similar to other transition-metal difluorides such as FeF2 but different to ZnF2 and MgF2, despite that the Co2+ size (ionic radius) is similar to Zn2+ and Mg2+. We found that the complete phase-transition sequence is tetragonal rutile (P42/mnm) → CaCl2 type (orthorhombic Pnnm) → distorted PdF2 (orthorhombic Pbca)+PdF2 (cubic Pa3¯) in coexistence → fluorite (cubic Fm3¯m) → cotunnite (orthorhombic Pnma). It was observed that the structural phase transition to the fluorite at 15 GPa involves a drastic change of coordination from sixfold octahedral to eightfold cubic with important modifications in the vibrational and electronic properties. We show that the stabilization of this high-pressure cubic phase is possible under nonhydrostatic conditions since ideal hydrostaticity would stabilize the distorted-fluorite structure (tetragonal I4/mmm) instead. Although the first rutile → CaCl2-type second-order phase transition is subtle by Raman spectroscopy, it was possible to define it through the broadening of the Eg Raman mode which is split in the CaCl2-type phase. First-principles DFT calculations are in fair agreement with the experimental Raman mode frequencies, thus providing an accurate description for all vibrational modes and elastic properties of CoF2 as a function of pressure