Pressure-induced dimerization kinetics of fullerene C60

Dimerization kinetics was studied for fullerene C₆₀ by IR spectroscopy at a pressure of 1.5 GPa in the temperature range 373–473 K. The kinetic curves for the formation of a dimer (C₆₀)₂ were obtained using its analytical IR band at 796 cm^?1. Under the assumption that pressure-induced C₆₀ dimerization is a second-order irreversible reaction, the reaction rate constants were determined at different temperatures. The corresponding activation energy and preexponential factor were found to be 134±6 kJ/mol and (1.74± 0.24)×10¹⁴ s^?1, respectively. The specific features of the solid-phase C₆₀ dimerization in simple cubic and face-centered cubic fullerite phases are discussed.     

Determination of the reaction rate constant and activation energy for pressure-induced 2+2 cycloaddition of the C60 fullerene

The kinetics of fullerene solid-phase dimerization proceeding through the 2+2 cycloaddition of C₆₀ at a pressure of 1.5 GPa is investigated by vibrational spectroscopy in the temperature range 373–473 K. Kinetic curves for the formation of (C₆₀)₂ dimers are obtained using the analytical band at 796 cm^?1 in the IR spectra of the (C₆₀)₂ dimer molecule. Under the assumption that the pressure-induced dimerization of C₆₀ is an irreversible second-order reaction, the reaction rate constants are determined at different temperatures. The activation energy and the preexponential factor are found to be equal to 134±6 kJ/mol and (1.74±0.24)×10¹⁴ s^?1, respectively.     

Pressure-induced polycondensation of C60 fullerene

Modifications of carbon which are formed from C₆₀ fullerite at pressures up to 10.0 GPa and temperatures up to 1900 K are studied by x-ray diffraction, Raman spectroscopy, and atomic force microscopy methods. The pressures p and temperatures T at which atomic, molecular, and polymolecular structures form under conditions of quasihydrostatic compression are determined. It is shown that, together with polymerization, another type of chemical interaction of the molecules, called polycondensation, which leads to the formation of polymolecular structures with a shortest intermolecular distance of 0.65 nm, is possible in the system. Three-dimensional polycondensation of C₆₀ fullerene is explained by the special properties of the new carbon states. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 10, 778–783 (25 May 1996) The spelling of the authors names are presented here in English as requested by the Russian Editorial office.     

Pressure-induced melting of charge-order in the self-doped mott insulator yttrium nickelate

The stability under pressure of the charge-density-wave in the insulating phase of YNiO₃ was studied by infrared spectroscopy and synchrotron diffraction techniques up to 23 GPa. YNiO₃ undergoes a pressure induced insulator-to-metal transition at approximately 15 GPa in the pressure domain, coinciding with the melting of the charge ordered phase. The optical band gap is non-zero above 15 GPa, as is the case above the reported insulator-metal transition (585 K) in the temperature-domain. There is a similarity between the infrared spectral profile around 15 GPa and the infrared spectral profile above ca. 700 K. We conclude therefore that the pressure-induced structural/electronic transition induced around 15 GPa, probably having an as-yet unreported counterpart in the temperature domain at a temperature in excess of 585 K.     

Electroconductivity and pressure–temperature states of step shocked C60 fullerite

A study of electrophysical and thermodynamic properties of C₆₀ single crystals under step shock loading has been carried out. The increase and the following reduction in specific electroconductivity of C₆₀ fullerite single crystals at step shock compression up to pressure 30 GPa have been measured. The equations of state for face centred cubic (fcc) C₆₀ fullerite as well as for two-dimensional polymer C₆₀ and for three-dimensional polymer C₆₀ (3D-C₆₀) were constructed. The pressure–temperature states of C₆₀ fullerite were calculated at step shock compression up to pressure 30 GPa and temperature 550 K. The X-ray diffraction studies of shock-recovered samples reveal a mixture of fcc C₆₀ and a X-ray amorphous component of fullerite C₆₀. The start of the formation of the X-ray amorphous component occurs at a pressure P _m≈ 19.8 GPa and a temperature T _m≈ 520 K. At pressures exceeding P _m and temperatures exceeding T _m, the shock compressed fullerite consist of a two-phase mixture of fcc C₆₀ fullerite and an X-ray amorphous component presumably consisting of the nucleators of polymer 3D-C₆₀ fullerite. The decrease in electroconductivity of fullerite can be explained by the percolation effect caused by the change of pressure, size and number of polymeric phase nuclei.     

Free and localized excitons in the luminescence spectrum of C60 crystals at high pressure

The luminescence spectra of C₆₀ single crystals are studied at T≅10 K and pressure up to 4.0 GPa. It is observed that as the pressure increases, one fine-structure band in the spectrum intensifies sharply and dominates at pressures P≥1.7 GPa. The pressure shift of this band is much larger than the shift of other bands in the spectrum, and its magnitude correlates with the pressure dependence of the band gap. It is shown that this band could be due to radiative recombination of free Frenkel excitons. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 3, 234–238 (10 August 1998)     

Mechanism of the formation of a diamond nanocomposite during transformations of C60 fullerite at high pressure

The results of an investigation of the transformation of C₆₀ fullerite to diamond under pressure through intermediate three-dimensionally polymerized and amorphous phases are reported. It is found that treatment of fullerite C₆₀ at pressures 12–14 GPa and temperatures ∼1400°C produces a nanocrystalline graphite-diamond composite with a concentration of the diamond component exceeding 50%. At lower temperatures (700–1200°C) nanocomposites consisting of diamondlike (sp ³) and graphitic (sp ²) amorphous phases are formed. The nanocomposites obtained have extremely high mechanical characteristics: hardness comparable to that of best diamond single crystals and fracture resistance two times greater than that of diamond. Mechanisms leading to the transformation of C₆₀ fullerite into diamond-based nanocomposites and the reasons for the high mechanical characteristics of these nanocomposites are discussed. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 11, 822–827 (10 June 1999)     

Physical and mechanical properties of C60 under high pressures and high temperatures

The physical and mechanical properties of a C₆₀ fullerene sample have been investigated under high pressure–high temperature conditions using a designer Diamond Anvil Cell. Electrical resistance measurements show evidence of C₆₀ cage collapse at 20 GPa, which leads to the formation of an insulating phase at higher pressure. Energy dispersive X-ray diffraction (EDXD) data indicated that the characteristic fcc reflections gradually decrease in intensity and eventually disappear above 28 GPa. A C₆₀ sample was laser-heated at a pressure of 35 GPa to a temperature of 1910±100 K and, subsequently, decompressed to ambient conditions. The photoluminescence spectra and the Raman spectrum of the pressure–temperature-treated sample were measured at a low temperature of 80 K. Raman peak at 1322.3 cm^?1 with full-width half-maximum of 2.9 cm^?1 was observed from the sample, which is attributed to the hexagonal diamond phase in the sample. The room temperature photoluminescence spectra showed a symmetric emission band centered in the red spectral range with a peak at 690 nm. The structural analysis of the pressure–temperature-processed C₆₀ sample using EDXD method showed strong internal structure orientation and a phase close to hexagonal diamond. Mechanical properties such as hardness and Young’s modulus were measured by nanoindentation technique and the values were found to be 90±7 and 1215±50 GPa, respectively and these values are characteristic of sp³-bonded carbon materials.     

Phase diagram of RDX (hexahydro-1,3,5-trinitro-s-triazine) at high pressures and temperatures

Abstract

The phase diagram of RDX-h₆ (hexahydro-1,3,5-trinito-s-triazine) and RDX-d₆ has been studied by Raman spectroscopy to more than 13 GPa at 295 K and 7.5 GPa between 150 and 450 K. Two stable high pressure phases have been found. γ-RDX or RDX-III forms from α-RDX above 3.8 GPa below 380 K. β-RDX forms when α- or γ-RDX are heated, can be retained metastably at low temperatues, and may be related to a very unstable form occasionally recovered at ambient pressure. Deuterium isotopic substitution and shear increase the temperature where β-RDX begins to form on heating.     

In situ Raman and photoluminescence study on pressure‐induced phase transition in C60 nanotubes

Single crystalline C₆₀ nanotubes having face‐centered‐cubic structure with diameters in the nanometer range were synthesized by a solution method. In situ Raman and photoluminescence spectroscopy under high pressure were employed to study the structural stabilities and transitions of the pristine C₆₀ nanotubes. A phase transition, probably because of the orientational ordering of C₆₀ molecules, from face‐centered‐cubic structure to simple cubic structure occurred at the pressure between 1.46 and 2.26 GPa. At above 20.41 GPa, the Raman spectrum became very diffuse and lost its fine structure in all wavenumber regions, and only two broad and asymmetry peaks initially centered at 1469 and 1570 cm^–1 were observed, indicating an occurrence of amorphization. This amorphous phase remained to be reversible until 31.1 GPa, and it became irreversible to the ambient pressure after the pressure cycle of 34.3 GPa was applied. Copyright © 2012 John Wiley & Sons, Ltd.     

Energy spectrum and phase transitions in C70 fullerite crystals at high pressure

Measurements have been made of the Raman, optical absorption, and luminescence spectra of single crystals and pellets of the fullerite C₇₀ at T=300 K and at pressures up to 12 GPa. The baric shift dω/dP and the Grüneisen parameters of the Raman-active intramolecular phonon modes have been determined. It has been established that the d ω/dP value for certain phonon modes abruptly changes at pressures of P ₁≈2 GPa and P ₂≈5.5 GPa, as do the half-widths of the Raman lines. These features in the Raman spectrum are associated with phase transitions at high pressure. The baric shifts of the absorption and luminescence edges of C₇₀ crystals have been determined and are −0.12 eV/GPa and −0.11 eV/GPa, respectively, for absorption and luminescence. The baric shift of the absorption edge decreases significantly with increasing pressure and is −0.03 eV/GPa at 10 GPa. These data have been used to determine the deformation potential of the fullerite C₇₀, which is about 2.1±0.1 eV. Zh. éksp. Teor. Fiz. 111, 262–273 (January 1997)     

Dimer and cluster formation in C60 photoreaction

The process of phototransformation in C₆₀ was analysed by means of Raman spectroscopy for single crystals irradiated at various temperatures between 80 K and 450 K. The activation window for the transformation process was found to be between the temperature of the first order phase transition of 260 K and an upper temperature of about 400 K. Detailed features of the resulting spectra were found to depend on the transformation temperature. From a comparison with ab initio calculations of Porezag et al. the material irradiated at high temperatures could be assigned to a C₆₀ dimer whereas the material phototransformed at room temperature could not be identified with a simple cluster.     

Thermodynamic properties of C<Subscript>60</Subscript> polyfullerites

This paper discusses the results of calorimetric studies of the 1D C₆₀ (orthorhombic) and 2D C₆₀ (tetragonal and rhombohedral) fullerites, as well as of the graphite-like polyfullerite, which are produced from a starting C₆₀ fullerite subjected to a pressure of 1–8 GPa at temperatures ranging from 300 to 1270 K. The analysis is made primarily of the C _p ⁰ heat capacity measurements performed in adiabatic calorimeters in the 5-to 350-K range.     

Crystal-field induced mixing of electron states in C60 crystals at high pressure

Optical absorption spectra of thin fullerene (C₆₀) crystals in the range 1.7 to 3.8 eV have been measured at T=300 K and at pressures up to 2.5 GPa. The spectrum shifts toward the red with pressure, and the electron absorption intensity is redistributed among its bands. The intensity of the band associated with the lowest direct electron interband transition monotonically increases with pressure, whereas the intensity of the upper interband feature decreases. Bands related to weak edge absorption in the range between 1.7 and 2.2 eV gradually merge with the band associated with the lowest interband transition, whose intensity rises with pressure. A similar redistribution of intensity among electron transition bands has been observed when comparing the spectrum of an isolated C₆₀ molecule and that of a C₆₀ crystal. The results indicate that the crystal-field induced mixing of electron states is present in solid C₆₀, and they can be discussed in terms of the Craig-McClure model, which was suggested to describe crystal-field induced mixing of electron states in anthracene and naphthalene molecular crystals. Zh. éksp. Teor. Fiz. 113, 313–322 (January 1998)     

Pressure induced anisotropic magnetovolume phenomena in Lu2Fe17 Intermetallics

Magnetisation and magnetic susceptibility of a Lu₂Fe₁₇ single crystal have been studied under hydrostatic pressure up to 1.2 GPa at temperatures down to 5 K using a SQUID magnetometer. The ferromagnetic phase of Lu₂Fe₁₇ is suppressed rapidly above a critical pressure P _C = 0.4 GPa in the whole temperature range below the critical temperature T _C . A magnetic phase diagram of Lu₂Fe₁₇ has been constructed using results of the magnetic susceptibility measurements under pressure. A pressure induced incommensurate antiferromagnetic phase exhibits metamagnetic transitions with the increasing critical magnetic field H _C under pressure. Taking into account recent neutron diffraction data, the pressure induced anisotropic changes of the lattice parameters of the Lu₂Fe₁₇ are discussed.     

Study of crystal and magnetic structures of manganite Pr<Subscript>0.7</Subscript>Ba<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at high pressure

The crystal and magnetic structures of manganite Pr_0.7Ba_0.3MnO₃ have been studied at high pressures of up to 5.1 GPa and temperatures from 10 to 300 K by means of the neutron diffraction. At normal pressure and a temperature T _C = 200 K, a ferromagnetic state forms in Pr_0.7Ba_0.3MnO₃. At high pressures P ≥ 1.9 GPa and T < T _N ≈ 153 K, a new antiferromagnetic state of A-type have been observed. Under high pressure, the Curie temperature T _C increases with the characteristic quantity dT _C/dP ≈ 2.4 K/GPa. A possible reason for the appearance of an A-type antiferromagnetic phase in Pr_0.7Ba_0.3MnO₃ at high pressures may be anisotropic uniaxial compression of oxygen octahedra along the b axis of the orthorhombic structure.     

Pressure and photo-induced phase transitions in sulphur investigated by Raman spectroscopy

Abstract

The phase transition of orthorhombic sulphur α-S₈ to a high pressure amorphous sulphur allotrope (a-S) has been investigated by Raman spectroscopy. The conversion is found to be induced by the absorption of laser light and can be discussed in terms of ring opening followed by cis-trans conversion of the dihedral angle of S₈ molecules. Laser energy and transition pressure are correlated due to the pressure tuned red shift of the absorption edge of α-S₈. The amorphous (a-S) phase is observed up to 15 GPa at laser intensities below 30μW/μm² at 514.5 and 488.0 nm. Above this threshold power a-S transforms into a second photo-induced phase (p-S), whose discrete Raman spectrum implies an ordered molecular and crystalline structure. By further increasing pressure crystalline S₆ can be created which is found to be the dominant molecular species at pressures above 10 GPa and low temperatures. A phase diagram in the range T < 300 K and p < 15 GPa is also presented.     

Distribution of light alkanes in the reaction of graphite hydrogenation at pressure of 0.1–7.8 GPa and temperatures of 1000–1350°C

ABSTRACT

We studied the effect of pressure and temperature on the hydrocarbon (HC) chain length distribution and total amount of HCs in the reaction of direct graphite hydrogenation at pressures of 0.1–7.8?GPa and temperatures of 1000–1350°C. An increase in pressure was found to lead both to an increase in the absolute yield of HCs due to direct graphite hydrogenation and to chain elongation of HC products. Light alkanes predominate among HCs in the entire studied range of P–T parameters. However, their concentration in quenched fluids increases as pressure is elevated, from less than 10?rel.% at 0.1?GPa to more than 40–50?rel.% at P?≥?3.8?GPa. Methane is actually the only light alkane among reaction products at 0.1?GPa and 1000°C, while it is a minor component at 7.8?GPa and 1350°C. The most stable alkane at pressures above 3.8?GPa is ethane (C₂H₆).     

Effect of high pressure on the crystal and magnetic structure and on the raman spectra in Pr<Subscript>0.7</Subscript>Ba<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> manganite

The crystal and magnetic structure and the Raman spectra in Pr_0.7Ba_0.3MnO₃ manganite have been studied by the neutron diffraction technique at pressures up to 5 GPa as well as by the X-ray diffraction and Raman spectroscopy at pressures up to 30 GPa. The pressure dependence is determined for the lattice parameters, unit cell volume, Mn-O bond lengths in the orthorhombic structure of the Imma symmetry, and bending and stretching vibration modes for oxygen octahedra. In the low-temperature range at pressure P = 1.9 GPa, the magnetic transition from the initial ferromagnetic (FM) ground state (T _C = 197 K) to the A-type antiferromagnetic (AFM) state (T _N = 153 K) has been revealed. The FM and AFM phases coexist at pressures up to 5.1 GPa and exhibit negative and positive values of the pressure coefficient for the Curie and Néel temperature, respectively (dT _C/dP = −2.3 K/GPa and dT _N/dP = 8 K/GPa). The pressure dependence of the Curie temperature in Pr_0.7Ba_0.3MnO₃ differs drastically from that observed in other manganites of nearly the same composition with the orthorhombic Pnma and rhombohedral R[`3]cR\bar 3c structures, where the FM phase is characterized by the positive values of dT _C/dP. The structural mechanisms of these phenomena are discussed.     

Ultraviolet Raman analysis of the formation of diamond from C60

The ultraviolet (257 nm) Raman spectrum of C₆₀ compressed to 30 GPa in a Mao–Bell diamond anvil cell with no pressure transmitting medium at ambient temperature indicates the formation of diamond after release of pressure. Previously, more extreme non-hydrostatic compression was reported to be required to form diamond from C₆₀. These results provide confirmation of the transformation of C₆₀ to diamond upon non-hydrostatic compression at room temperature and illustrate the utility of UV Raman spectroscopy for the analysis of carbon phases containing both sp² and sp³ bonding.