Diamond: electronic ground state of carbon at temperatures approaching 0 K.

  title={Diamond: electronic ground state of carbon at temperatures approaching 0 K.},
  author={Wojciech Grochala},
  journal={Angewandte Chemie},
  volume={53 14},
  • W. Grochala
  • Published 1 April 2014
  • Chemistry, Materials Science
  • Angewandte Chemie
The relative stability of graphite and diamond is revisited with hybrid density functional theory calculations. The electronic energy of diamond is computed to be more negative by 1.1 kJ mol(-1) than that of graphite at T=0 K and in the absence of external pressure. Graphite gains thermodynamic stability over diamond at 298 K only because of the differences in the zero-point energy, specific heat, and entropy terms for both polymorphs. 

Figures and Tables from this paper

Relative Thermodynamic Stability of Diamond and Graphite.
This work reinvestigate the relative thermodynamic stability of diamond and graphite and found that for T < 400 K, graphite is always more stable than diamond at ambient pressure.
Relative stability of diamond and graphite as seen through bonds and hybridizations.
This work considers an analytical model to gain fundamental insight into the reasons for the quasi-degeneracy of diamond and graphite despite their extremely different covalent bonding patterns and derives the allotropes' relative energies.
Absent Diamond-to-β-Sn Phase Transition for Carbon: Quantum Chemical Topology Approach
Several quantum chemical topology indicators (bond paths, electron density values at bond critical points, delocalization indices, interaction energies, electron localizability indicator) are used to
Towards a metallic quasi‐d9 system without copper: AgO at high pressure
AgO is a prototypical mixed‐valence compound, with markedly different coordination environment of dumbbell Ag(1+) and low‐spin square‐planar Ag(3+) which render it a narrow band gap semiconductor.
On the DFT ground state of crystalline bromine and iodine.
Poor performance of economic DFT functionals should be kept in mind, for example, during global structure optimizations of systems with significant contributions from halogen bonds, because of the erroneous ground state within common density functional theory methods.
First-Principles Study of the Structural, Electronic, Dynamic, and Mechanical Properties of HOPG and Diamond: Influence of Exchange–Correlation Functionals and Dispersion Interactions
Various properties of two polymorphs of carbon, highly oriented pyrolytic graphite (HOPG) and diamond, were investigated at the ab initio level using different Hamiltonians with all-electron
Ab initio calculations of carbon and boron nitride allotropes and their structural phase transitions using periodic coupled cluster theory
We present an ab-initio study of boron nitride as well as carbon allotropes. Their relative thermodynamic stabilities and structural phase transitions from low- to high-density phases are
Global Search for Crystal Structures of Carbon under High Pressure
A systematic search for structures of carbon crystals under high pressure was performed by using the artificial force induced reaction method including periodic boundary conditions, and new structures that were denser than diamond were obtained at 100 GPa.
From small fullerenes to the graphene limit: A harmonic force‐field method for fullerenes and a comparison to density functional calculations for Goldberg–Coxeter fullerenes up to C980
A simple but computationally very efficient harmonic force field is introduced, which works for all fullerene structures and includes bond stretching, bending, and torsional motions as implemented into the authors' open‐source code Fullerene, making it possible to extrapolate to the graphene limit.
Deductive molecular mechanics of carbon allotropes (Review article)
The relative stability of diamond and graphite is readdressed from the new perspective of deductive molecular mechanics. Unlike most theoretical studies that are conducted numerically, this article


Structural theory of graphite and graphitic silicon
The graphitic phases of C and Si are studied with the use of the pseudopotential local-density-functional approach. For graphite, good agreement with experiment is obtained for the in-plane lattice
On the correlation energy of graphite
The correlation energy per atom of a graphite layer is determined by means of increments obtained in ab initio calculations for aromatic molecules with various numbers of correlated localized σ and π
Diamond‐Graphite Equilibrium Line from Growth and Graphitization of Diamond
Diamond growth occurs at high temperatures and pressures in the presence of certain molten metals which serve as solvent catalysts. The zones of pressure and temperature in which diamond growth
Thermal Expansion Coefficient of Synthetic Diamond Single Crystal at Low Temperatures
The lattice parameter of synthetic diamond single crystals has been measured in the range 4.2-320 K by the X-ray diffraction method. The lattice parameter is found to be nearly constant between 4.2
Hypothetical hard structures of carbon with cubic symmetry
In this work we performed ab initio pseudopotential, density functional calculations of the structure and electronic properties of two hypothetical carbon structures with cubic symmetry: C6 bcc, body
Heat Capacity of Diamond at High Temperatures
The enthalpy of gem diamonds has been measured from 273° to 1073°K using a ``drop'' method and a Bunsen ice calorimeter. The derived heat‐capacity values, which are believed to be accurate to ±0.5%,
Thermodynamic stability of boron: the role of defects and zero point motion.
D density functional calculations in the generalized gradient approximation are used to study a broad range of possible beta-rhombohedral structures containing interstitial atoms and partially occupied sites within a 105 atoms framework, finding the two most stable structures are practically degenerate in energy and semiconducting.
Symmetry-broken crystal structure of elemental boron at low temperature
The crystal structure of boron is unique among chemical elements, highly complex, and imperfectly known. Experimentalists report the �-rhombohedral (black) form is stable over all temperatures from
n-diamond: an intermediate state between rhombohedral graphite and diamond?
A powder sample of n-diamond (new-diamond) synthesized from Fe-catalysed carbon black was investigated using the x-ray diffraction (XRD) technique. Based on the analysis and simulation of the peak
ERRATUM: A theoretical study of the smallest tetrahedral carbon schwarzites
We present a tight-binding molecular-dynamics investigation on the structural, elastic and electronic properties of the smallest periodic tetrahedral carbon schwarzites fcc-(C28)2, fcc-(C36)2 and