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H. M. Fretwell J. A. Duffy M. A. Alam R. Evans 《Journal of Radioanalytical and Nuclear Chemistry》1996,210(2):575-582
In this paper we present our recent positron annihilation study of the liquid»solid phase boundary for CO2 confined in nanometer pores of VYCOR glass. We find that CO2 remains liquid in the pores far below the bulk freezing temperature and there is pronounced hysteresis between freezing and melting compared to that seen at the gas-liquid boundary in the pores. On freezing we see evidence of open space created in the pores. This leads to complex melting behaviour possibly involving the formation of gas-liquid interfaces. We see that frezing in the pores is totally irreversible, so that any solid which forms (no matter how small) remains stable up to the higher melting temperature. In contrast melting is more reversible (possibly indicating nucleation centres which permit immediate re-freezing). Finally, the pre-frozen state in the pores is different to the post-melted state. 相似文献
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J. A. Duffy H. M. Fretwell A. P. Clarke S. B. Dugdale M. A. Alam 《Journal of Radioanalytical and Nuclear Chemistry》1996,211(1):173-179
The phase behaviour of carbon dioxide confined in VYCOR glass at pressures below that of the bulk triple point (0.51 MPa) has been investigated. The temperature at which freezing occurs appears to be pressure dependent below 0.3 MPa. As experiments are performed at successively lower pressures, the confined phase transitions gradually disappear, due to either partial pore filling, or the proximity of the confined triple point. 相似文献
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M. A. Alam H. M. Fretwell J. A. Duffy A. P. Clarke S. B. Dugdale 《Journal of Radioanalytical and Nuclear Chemistry》1996,210(2):255-271
In this paper we present a brief review of the current state of positron annihilation research into the phase behaviour of fluids confined within restricted boundaries. We summarise, in the form of selected examples, the work done so far on: (1) fluids confined in the nanometer-size pores of VYCOR glass, with particular emphasis on the confined phase diagram and the mechanisms behind phase transitions compared to bulk. (2) The adsorption/physisorption of gases on internal surfaces of grafoil and the potential of positron technique for revealing physical properties, such as the intricate molecular arrangements during phase transitions of the layered fluid. 相似文献
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The Feynman path integral Monte Carlo approach has been coupled to the gauge including atomic orbital formalism in order to analyse the absolute magnetic shieldings of the benzene nuclei under the conditions of thermal equilibrium. The Hamiltonian employed in the derivation of ensemble averaged NMR quantities is of the Hartree-Fock type. The basis set used is of 6–31G quality. The spatial delocalization of the atoms leads to a deshielding of both types of benzene nuclei relative to the shieldings experienced at the minimum of the potential energy surface. This deshielding has to be traced back to bond length elongations in thermal equilibrium. The influence of the nuclear fluctuations on the NMR parameters of benzene is quantum driven up to temperatures of 400 K; classical fluctuations are of minor importance in this low-temperature window. 相似文献
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Kondo T Khasanov R Karpinski J Kazakov SM Zhigadlo ND Ohta T Fretwell HM Palczewski AD Koll JD Mesot J Rotenberg E Keller H Kaminski A 《Physical review letters》2007,98(15):157002
We use microprobe angle-resolved photoemission spectroscopy (microARPES) to separately investigate the electronic properties of CuO2 planes and CuO chains in the high temperature superconductor, YBa2Cu4O8. For the CuO2 planes, a two-dimensional (2D) electronic structure is observed and, in contrast to Bi2Sr2CaCu2O8+delta, the bilayer splitting is almost isotropic and 50% larger, which strongly suggests that bilayer splitting has no direct effect on the superconducting properties. In addition, the scattering rate for the bonding band is about 1.5 times stronger than the antibonding band and is independent of momentum. For the CuO chains, the electronic structure is quasi-one-dimensional and consists of a conduction and insulating band. Finally, we find that the conduction electrons are well confined within the planes and chains with a nontrivial hybridization. 相似文献
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Chatterjee U Shi M Kaminski A Kanigel A Fretwell HM Terashima K Takahashi T Rosenkranz S Li ZZ Raffy H Santander-Syro A Kadowaki K Norman MR Randeria M Campuzano JC 《Physical review letters》2006,96(10):107006
The autocorrelation of angle resolved photoemission data from the high temperature superconductor Bi(2)Sr(2)CaCu(2)O(8+delta) shows distinct peaks in momentum space which disperse with binding energy in the superconducting state, but not in the pseudogap phase. Although it is tempting to attribute a nondispersive behavior in momentum space to charge ordering, a deconstruction of the autocorrelation reveals that the nondispersive peaks arise from the tips of the Fermi arcs, which themselves do not change with binding energy. 相似文献