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Chris J. Pickard

Publications and source records attributed to Chris J. Pickard.

117 records · Page 7Linked to original sources

A First Principles Theory of Nuclear Magnetic Resonance J-Coupling in solid-state systems

A method to calculate NMR J-coupling constants from first principles in extended systems is presented. It is based on density functional theory and is formulated within a planewave-pseudopotential framework. The all-electron properties are recovered using the projector augmented wave approach. The method is validated by comparison with existing quantum chemical calculations of solution-state systems and with experimental data. The approach has been applied to verify measured J-coupling in a silicophosphate structure, Si5O(PO4)6

cond-mat.mtrl-sci↗

Graphite intercalation compounds under pressure

Motivated by recent experimental work, we use first-principles density functional theory methods to conduct an extensive search for low enthalpy structures of C$_6$Ca under pressure. As well as a range of buckled structures, which are energetically competitive over an intermediate range of pressures, we show that the high pressure system ($\gtrsim 18$ GPa) is unstable towards the formation of a novel class of layered structures, with the most stable compound involving carbon sheets containing five- and eight-membered rings. As well as discussing the energetics of the different classes of low enthalpy structures, we comment on the electronic structure of the high pressure compound and its implications for superconductivity.

cond-mat.supr-con↗

High-pressure phases of silane

It has been suggested that hydrogen may metallise at lower pressures if it is ``precompressed''. Here we introduce a search strategy for predicting high-pressure structures and apply it to silane using first-principles electronic structure computations. It is based on relaxing randomly chosen structures, and is demonstrated to work well for unit cells containing up to at least ten atoms. We predict that silane will metallise at higher pressures than previously anticipated, but we suggest that the metallic phase might show high-temperature superconductivity at experimentally accessible pressures.

cond-mat.mtrl-sci↗

Electronic structure of superconducting graphite intercalate compounds: The role of the interlayer state

Although not an intrinsic superconductor, it has been long--known that, when intercalated with certain dopants, graphite is capable of exhibiting superconductivity. Of the family of graphite--based materials which are known to superconduct, perhaps the most well--studied are the alkali metal--graphite intercalation compounds (GIC) and, of these, the most easily fabricated is the C${}_8$K system which exhibits a transition temperature $\bm{T_c\simeq 0.14} $K. By increasing the alkali metal concentration (through high pressure fabrication techniques), the transition temperature has been shown to increase to as much as $\bm 5 $K in C${}_2$Na. Lately, in an important recent development, Weller \emph{et al.} have shown that, at ambient conditions, the intercalated compounds \cyb and \cca exhibit superconductivity with transition temperatures $\bm{T_c\simeq 6.5} $K and $\bm{11.5} $K respectively, in excess of that presently reported for other graphite--based compounds. We explore the architecture of the states near the Fermi level and identify characteristics of the electronic band structure generic to GICs. As expected, we find that charge transfer from the intercalant atoms to the graphene sheets results in the occupation of the $\bmπ$--bands. Yet, remarkably, in all those -- and only those -- compounds that superconduct, we find that an interlayer state, which is well separated from the carbon sheets, also becomes occupied. We show that the energy of the interlayer band is controlled by a combination of its occupancy and the separation between the carbon layers.

cond-mat.supr-con↗

Nonlocal pseudopotentials and magnetic fields

We show how to describe the coupling of electrons to non-uniform magnetic fields in the framework of the widely used norm-conserving pseudopotential appro ximation for electronic structure calculations. Our derivation applies to magnetic fields that are smooth on the scale of the core region. The method is validated by application to the calculation of the magnetic susceptibility of molecules. Our results are compared with high quality all electron quantum chemical results, and another recently proposed formalism.

cond-mat↗

First principles theory of the EPR g-tensor in solids: defects in quartz

A theory for the reliable prediction of the EPR g-tensor for paramagnetic defects in solids is presented. It is based on density functional theory and on the gauge including projector augmented wave (GIPAW) approach to the calculation of all-electron magnetic response. The method is validated by comparison with existing quantum chemical and experimental data for a selection of diatomic radicals. We thenperform the first prediction of EPR ${\rm g} $-tensors in the solid state and find the results to be in excellent agreement with experiment for the $E'_1$ and substitutional P defect centers in quartz.

cond-mat.mtrl-sci↗

Accurate kinetic energy evaluation in electronic structure calculations with localised functions on real space grids

We present a method for calculating the kinetic energy of localised functions represented on a regular real space grid. This method uses fast Fourier transforms applied to restricted regions commensurate with the simulation cell and is applicable to grids of any symmetry. In the limit of large systems it scales linearly with system size. Comparison with the finite difference approach shows that our method offers significant improvements in accuracy without loss of efficiency.

cond-mat.mtrl-sci↗

Cubic boron nitride: an experimental and theoretical ELNES study

A comparison between experimental and theoretical electron Energy Loss Near Edge Structure (ELNES) of B and N K-edges in cubic boron nitride is presented. The electron energy loss spectra of cubic boron nitride particles were measured using a scanning transmission electron microscope. The theoretical calculation of the ELNES was performed within the framework of density functional theory including single particle core-hole effects. It is found that experimental and calculated ELNES of both the B and N K-edges in cubic boron nitride show excellent agreement.

cond-mat.mtrl-sci↗

All-electron magnetic response with pseudopotentials: NMR chemical shifts

A theory for the ab initio calculation of all-electron NMR chemical shifts in insulators using pseudopotentials is presented. It is formulated for both finite and infinitely periodic systems and is based on an extension to the Projector Augmented Wave approach of Bloechl [P. E. Bloechl, Phys. Rev. B 50, 17953 (1994)] and the method of Mauri et al [F. Mauri, B.G. Pfrommer, and S.G. Louie, Phys. Rev. Lett. 77, 5300 (1996)]. The theory is successfully validated for molecules by comparison with a selection of quantum chemical results, and in periodic systems by comparison with plane-wave all-electron results for diamond.

cond-mat.mtrl-sci↗