electron emission from diamondoids a diffusion quantum monte.ppt

Real Systems There have been many important applications of QMC to model systems (e.g. electron gases, jellium surfaces and spheres). Real systems (atoms, molecules and solids) usually require more computational effort. QMC is most accurate first-principles total-energy method for systems of more than a few tens of electrons. QMC is becoming an important tool in ab initio studies of real systems. Electronic-Structure Methods Outline of Talk + References QMC studies of solid diamond [Maezono et al., PRL 98, 025701]. QMC studies of solid neon [Drummond Needs, PRB 73, 024107]. QMC calculations of optoelectronic properties of diamondoids [Drummond et al., PRL 95, 096801]. Ex nihilo structure prediction (silane solid hydrogen) [Pickard Needs PRL 97, 045504; Pickard Needs, Nature Physics (online)] Solid Diamond Zero-temperature equation of state of diamond is imperfectly characterised. Knowledge of EoS is important in design of diamond anvil cells. Raman frequency: zone-centre optic-phonon frequency, measured in Raman spectroscopy. Raman spectroscopy of diamond could be used as a pressure gauge if Raman frequency as a function of pressure were known Use QMC to calculate EoS and Raman frequency of diamond. Designing the Calculations Calculate QMC energy at different volumes and fit Vinet EoS. Like particle-physics experiments, QMC calculations are expensive. Simulate fitting of EoS to data from DFT EoS with added noise and identify the volume range that allows the EoS parameters to be determined with maximum accuracy. The QMC Calculations Use Dirac-Fock pseudopotentials for C4+ cores. Use simulation cells consisting of 4×4×4 5×5×5 primitive cells (128 250 atoms). Use plane-wave DFT calculations, then re-express orbitals in a blip basis. Single-particle finite-size errors are small; extrapolate to infinite system size using E(N)=E(∞)+b/N. Add DFT quasiharmonic free energy at 300 K. Compare with experimental results: McSkimin Andreatch, J. Appl. Phys. 43, 2944; Occel