Modeling materials and processes with VASP: From spintronics to catalysis

1. Modeling materials and processes with VASP: From spintronics to catalysis

2. Overview I • The prehistory of VASP • Getting started • From pseudopotentials to all-electron calculations • Current developements: • Towards post-DFT approaches

3. Overview II A quantum perspective to materials science A – DFT applied to materials science • Complex intermetallic alloys • Vibrational spectroscopy of DNA bases • Nanostructured magnetic materials for spintronics • Bimetallic catalysts for selective hydrogenation • Nanoporous materials: molecular reactions in zeolites B -- Post-DFT studies • Strongly correlated transition-metal oxides – DFT +U • Hybrid functionals applied to molecules and solids

4. The prehistory of VASP Car-Parrinello ab-initio MD - 1985 - Total energy minimization via dynamical simulated annealing - Adiabatic propagation of electronic orbitals via pseudo-Newtonian dynamics - Control of adiabaticity for metallic systems ? Conjugate gradient minimization of total energy -1989 - Dynamics on the Born-Oppenheimer surface - Slow convergence or even instability for metallic systems (``charge sloshing´´)

5. Getting started: 1991-1993 Learning from precursors - Remain on the Born-Oppenheimer surface - Improve stability and convergence for metals - Iterative diagonalization - Conjugate gradient minimization of eigenvalues or residuum minimization - Optimized charge- and spin-mixing Improve basis-set convergence - Optimized ultrasoft pseudopotentials - Data-base of potentials for all elements

6. Making a high-performance code 1995-99 Migration to F90 and Parallelization - MPI-based, highly transportable code Spin-polarized version for magnetic systems Avoid limitations due to pseudopotentials - Full-potential version based on projector–augmented waves

7. G.Kresse and J. Hafner, Phys. Rev. B 47,558 (1993) G. Kresse and J. Furthmüller, Phys. Rev. B 54, 111969 (1996); Comput. Mater. Sci. 6, 15 (1996) G. Kresse and D. Joubert, Phys. Rev. B 59, 1758 (1999).

8. Principal features of VASP - I • (Spin)-Density Functional Theory (and beyond) • -The ‚Jacobs ladder‘ of DFT • - Local (spin-)density approximation (L(S)DA) • - Generalized gradient approximation (GGA) – PW91, (R)PBE • - Meta-GGA • - Hybrid functionals (HSE03, PBE0) • - Exact and screened exchange • - LDA+U for strongly correlated systems • - Scalar-relativistic + spin-orbit coupling • - Unconstrained noncollinear magnetism • - Orbital polarization

9. Principal features of VASP - II • Plane-wave basis set • - Norm-conserving (NC) and ultrasoft (US) pseudopotentials • - Projector-augmented-wave (PAW) full-potential treatment • - PP and PAW data base for all elements (including lanthanides • and actinides) • Efficient iterative diagonalization of the Hamiltonian • - Minimization of norm of residual vector to each eigenstate or • conjugate-gradient minimization of eigenvalues • - Optimized charge- and spin-density mixing • Exact calculation of Hellmann-Feynman forces and stresses • - Static optimization of unit cell and atomic positions • - Molecular dynamics in the microcanonical and canonical • ensembles (Nose dynamics) • Graphical user interface and visualization tools

10. Principal features of VASP - III • Tool-box Electronic band structure and density of states, partial DOS Charge- and spin-densities Photoelectron spectroscopy (incl. core levels) Optical spectroscopy Polarizability STM simulations Phonons in solids Molecular vibrational spectroscopy Transition-state search, calculation of reaction rates • Limitations Electronic structure and static structure optimization for systems with up to 10000 valence electrons) Ab-initio MD for systems with up to about 3000 valence electrons ) extending over 50 – 80 ps

11. VASP – Current developments • Exact exchange and hybrid functionals Hybrid functionals (HSE0, PBE0) Exact and screened exchange New functionals • All-electron (valence plus core) PAW approach • Transformation to most localized Wannier orbitals • Approximate treatment of vdW forces within DFT • Many-body perturbation theory (GW) • Additions to tool box Polarizability, dielectric constant, Born effective charges Many-body perturbation theory (GW) Electric field gradients, NMR spectra Electronic transport Magnetic anisotropy ... and the next generation of codes beyond VASP !

12. Current applications of within the CMS group Complex magnetism Nanostructured magnets, noncollinear magnetism Intermetallic compounds and alloys Mechanical properties, embrittlement, quasicrystals Molten metals and alloys Chemical order in Zintl alloys Surface science, catalysis and corrosion Metals and alloys, oxides, sulfides Zeolites and related materials Acid-based catalysis: Bronsted- and Lewis sites Nanotubes and related materials

13. Current status of usership throughout the world • Cooperation with Material Design SA • No maintenance, no support licences from Univ. Wien • About 50 industrial site-licences • More than 500 academic site-licences (universities and public • non-profit research laboratories)

14. Current applications of worldwide: Materials: Semiconductors and insulators Ferrolelectrics Glasses, ceramics and minerals Metals, alloys and intermetallic compounds Magnetic materials Molecular crystals Fullerenes and nanotubes ........................... Properties and processes: Mechanical properties: elasticity and plasicity Phonons and thermodynamics Theoretical crystallography, mineralogy Heterogeneous catalysis: oxidation, hydrogenation, hydrodesulfurization, isomerization cracking Electrochemistry and electrocatalysis .............................

15. Case studies based on I. DFT calculations • Complex intermetallic compounds • Components of Al-rich high-strength alloys • Surfaces of quasicrystals • STM studies of fivefold surfaces of icosahedral AlPdMn • Vibrational spectroscopy of molecules and solids • Crystalline DNA bases • An old problem and computational tour de force: • Crystalline and magnetic structure of Mn • Nanostructured magnetic materials: • Ultrathin films, nanowires and clusters • Selective hydrogenation on bimetallic catalysts: • Conversion of unsaturated aldehydes to unsaturated alcohols • Molecular reactions in zeolites: • Beckmann rearrangement of cyclohexanoneto caprolactam

16. Al-rich nanocrystalline high-strength alloys • Nanocrystalline Al94V4Fe2 has a tensile strength of 1300 MPa, exceeding the strength of usual technical steels • The alloys consist of crystalline Al-rich compounds in a partially amorphous matrix – here we analyze the bonding properties of Al10V • 3D-Kagome-network with V atoms at vertices, Al2 atoms in the centers of V-V links • Large voids occupied by Friauf polyhedra of 4 Al1 and 12 Al3 atoms cF176 crystal structure of Al10V Space group Fd3m (No 227) Al10V-structure = ´´super-Laves phase´´ of MgCu2 type: Mg atoms are replaced by Friauf clusters of Al1 and Al3, Cu atoms by V atoms linked by Al2 atoms

17. Covalent bonding in Al10V: ...V-Al-V-Al-... chains Total electron density (left) and difference-electron density (right) along the .....–V-Al2-V-Al2-.... chains in the Al10V structure

18. Covalent bonding in Al10V: Friauf-polyhedra Total electron density (left) and difference-electron density (right) In a plane cutting across the Friauf-polyhedra. Maxima in the difference-electron density mark covalent bonds between Al3 atoms

19. Phase stability of Al-rich Al-V compounds • Heat of formation of Al-rich Al-V compounds (the solid line connects pure Al and Al3V): • Filling the center of the Friauf polyhedra with Al is energetically unfavorable • Other Al-rich compounds have comparable heats of formation

20. Quasicrystals • Quasicrystals are ordered structures without translational periodicity and non-crystallographic (icosahedral, decagonal, ....) symmetry • Quasicrystalline structures may be constructed by a cut-and-projection techniques from higher dimensions, e.g. projecting a hypercube in 6D onto the vertices of an icosahedron • A hierarchy of periodic structures („rational approximants“) systematically approaching the quasiperiodic limit may be constructed by replacing in the vectors defining the icosahedral vertices the Golden Mean t by a ratio of Fibonacci numbers: Fn+1/Fn= 1/1, 2/1, 3/2, 5/3, ................. t ~ 1.6180... • Icosahedral AlPdMn: 1/1 approximant 128 atoms/cell • 2/1 approximant 542 atoms/cell

21. Structure of icosahedral quasicrystals Structure model for face-centred icosahedral Al-Pd-Re(Mn) in 6D: quasiperiodic structure determined by projection of 6D acceptance domains on physical space, chemical order determined by shell-structure of atomic surfaces. Structure in real space: Interpenetrating Mackay- and Friauf- clusters – imaging by scanning tunneling microscopy ?

22. Structure of quasicrystals and quasicrystalline surfaces Tiling model (left) and electron-density map (right) of a fivefold surface of a stable icosahedral AlPdMn quasicrystal

23. Structure of quasicrystals and quasicrystalline surfacesModeling of quasicrystalline surface: Low-order (2/1) approximant, periodic slab model >> ~ 540 atoms/cell Simulated STM images of characteristic structural features observed on the 5-fold surfaces of i-AlPdMn: the ‚white flower‘ and the ‚dark hole‘, together with the underlying tiling model M. Krajci and J.H., Phys. Rev. B 71 (2005) 054202 M. Krajci, J.H., J. Ledieu and R. McGrath, Phys. Rev. B (submitted)

24. Structure and vibrational spectra of molecular crystals • Understanding the vibrational spectra of crystalline DNA bases • Influence of intermolecular bonding based on hydrogen bonds • Positions of protons not very well determined by diffraction experiment >>>> Optimization of crystal structure using VASP >>>> Calculation of vibrational eigenfrequencies and eigenvectors using ab-initio force constants M.Plazanet, N. Fukushima and M. Johnson, Chem. Phys. 280(2002) 53

25. Structure and vibrational spectra of molecular crystals Calculated and measured INS spectra: (a) experiment, (b) calculated with fully relaxed cell geometry and internal coordinates, (c) and (d) calculated for LT and HT structures after coordinate optimization only Crystal structure of thymine

26. Structure and vibrational spectra of molecular crystals Eigenvectors of characteristic vibrational eigenmodes of thymine

27. Crystalline and magnetic structure of Mn a-Mn T>TN : PM, cubic A12 – cI58 – I43m, isostructural to g-Mg17Al12 T<TN : noncollinear AFM, tetragonal I42m, magnetic space-group PI43m or subgroup D. Hobbs, J. Hafner, and D. Spisak, Phys. Rev. B 68, 014407 (2003)

28. Complex reconstructions of ultrathin g-Fe films onCu(100) Atomically resolved STM images of 2 – 4 ML films • STM images of films grown at 300K • 3ML film with (1x4) stripes and (1x1) domains • 4ML film with (1x6) domains STM : A.Biedermann et al., PRL 86, 464 (2001) PRL 87,086103 (2001) LEED: S. Müller et al., PRL 74, 765 (1995)

29. Complex reconstructions of ultrathin g-Fe films onCu(100) • Computational strategy: • Model system by thick slabs (up to 15 monolayers) with large • surface cells • Use generalized gradient approximation (mandatory for • magnetic systems) • Simultaneous optimization of all structural and magnetic • degrees of freedom

30. Complex reconstruction of ultrathin g-Fe films on Cu(100) Shear instability of fct Fe along the Bain path a=3.40 A (minimizing the total energy of ferromagnetic fct Fe) Epitaxial constraint: a=aCu=3.637 Angstr. Ferromagnetic c/a=1.0, d=0.259 Angstr., a=14.5° Bilayer antiferrom. c/a=0.99, d=0.128 Angstr., a=7.3° Antiferromagnetic c/a=0.97, d=0.077 Angstr., a=4.4° Paramagnetic c/a=0.90, d=0.045 Angstr., a=2.6° Strong correlation between lattice distortion and magnetism !

31. Complex reconstruction of ultrathin g-Fe films on Cu(100) (1x4) reconstruction of the Fe surface Total energy of 1-, 3-ML films (FM), and of a 6-ML film (bilayer AFM) as a function of the shearing of the surface layer Layer-resolved lateraldisplacements in a (1x4) reconstructed FM 3ML Fe/Cu(100) film Shear angle 13° (calc.), 14° (STM) Vertical buckling Dz =0.18 Angst. (calculation and LEED)

32. Complex reconstruction of ultrathin g-Fe films on Cu(100) (1x2) reconstruction of a bilayer-antiferromagnetic 6ML Fe/Cu(100) film: - Only surface layer reconstructs, shear angle 13.5° - Deeper layers are rigidly shifted along x direction . • All g-Fe films on Cu(100) are instable against monoclinic shear • Shearing increases with increasing ferromagnetic character • 3ML: Shearing reduced in deeper layers due to epitaxial constraint • 6ML: Deeper layers only rigidly shifted D. Spisak and J.H., PRL 88,056101 (2002)

33. Complex reconstruction of ultrathin g-Fe films on Cu(111) • Stable fcc films up to 6 ML by pulsed laser deposition • High-spin ferromagnetism up to 3 ML • Low-spin ferrimagnetic state for 4 to 6 ML • Bilayer antiferromagnetic order with [100] stacking sequence is also the magnetic ground-state in 4ML Fe/Cu(111) films • Magnetic energy difference relative to FM state 223 meV/atom • BAFM[100] ordering reduces geometric distortions . D. Spisak and J.H., PRB 67, 1334434 (2003)

34. Transition-metal clusters I • Determine cluster geometry • Determine magnetic ground-state • Role of orbital moments Fully relativistic calculation: spin-orbit coupling and non-collinearity Spin-moment Orbital moment Pt5-cluster • Magnetic moments • -perp. to 3-fold axis • S=5.6 mB, L=1.0 mB • parallel 3-fold axis • S=5.6 mB, L=1.2 mB • MAE = 5 meV/atom

35. Transition-metal clusters II Spin-moment Orbital moment Pt6-cluster • Magnetic moments • S=6.9 mB, L=1.3 mB • S=6.4 mB, L=1.7 mB • MAE = 4 meV/atom Local spin- and orbital moments noncollinear, but cluster moments aligned T. Futschek, M. Marsman, J.H., to be published

36. Nanostructured magnetic materials for spintronics • Ab-initio simulations allow access to locally resolved magnetic information not available from experiment • Exploration of structure/property relationship • Modelling of complex reconstructions • Fast exploration of novel materials: nanostripes, nanowires, clusters

37. Surface science and catalysis Bimetallic catalysts: Selective hydrogenation of unsaturated aldehydes to unsaturated alcohols on Pt-Fe – origin of selectivity ? Acid-based catalysis in zeolites: Beckmann rearrangement of cyclohexanone to e-caprolactam – nature of the active sites ? • Computational strategy: • Use slab-models with large surface cells for the surfaces of metallic • catalysts and periodic models for zeolites • Explore possible all adsorption configurations of reactants, perform • transition-state, use harmonic transition-state theory for reaction rates • Theoretical ‚in-situ‘ spectroscopy for comparison with experiment

38. Selective hydrogenation on bimetallic catalysts a,b-unsaturated aldehydes (a) acrolein (2-propenal) (b) crotonaldehyde (2-butenal) (c) Prenal (3-methyl-2-butenal) Hydrogenation of C=O double-bond: unsaturated alcohols Hydrogenation of C=C double-bond: saturated aldehydes Pt-catalysts: low selectivity Bimetallic Pt-Fe and Pt-Sn: improved selectivity R. Hirschl, F. Delbecq, Ph. Sautet, J.H., J. Catal., 217, 354 (2003).

39. Selective hydrogenation on bimetallic catalysts Surface of Pt-Fe catalysts UHV studies and DFT calculations: Pt segregates at surface: Origin of selectivity ???? Adsorption studies: strong Fe-O interaction partially reverses segregation, creates active Fe-sites in surface

40. Selective hydrogenation on bimetallic catalysts Adsorption modes of a,b-unsaturated aldehydes on a metal surface disCO disCC Pt 1.042 Pt/PtFe 0.584 Fe/PtFe 0.482 Pt 0.248 Pt/PtFe 0.004 -0.077 Fe/PtFe 0.681 0.688 h4-trans top Pt Pt/PtFe 0.126 Fe/PtFe 0.558 0.383 Pt1.134 0.671 Pt/PtFe 0.628 0.180 Fe/PtFe 1.247 0.788 h3-cis dis-14 Pt Pt/PtFe 0.425 Fe/PtFe 1.090 0.679 Pt Pt/PtFe 0.7680.155 Fe/PtFe 1.476 0.971 Adsorption energies at 1/12 coverage: Acrolein / Prenal

41. Selective hydrogenation on bimetallic catalysts • Strong differences in adsorption energies on Pt/PtFe and Fe/PtFe surfaces partially reverses surface segration: Quasichemical model • Strong Fe-O interaction activates C=O double bond

42. Selective hydrogenation on bimetallic catalysts • Strong Fe-O interaction activates C=O double bond Prenal adsorbed in h3-configuration on a segregated Pt/PtFe surface (left) and at a Fe atom in a Fe/PtFe surface. Difference electron densities: dark – charge influx, bright – charge depletion

43. Selective hydrogenation on bimetallic catalysts • Vibrational spectroscopy of reactants (prenal) Reaction scenario can be verified by in-situ spectroscopy

44. Selective hydrogenation on bimetallic catalysts • Strong interaction with reactant modifies surface of catalyst • Strong Fe-O interaction activates C=O double bond • Fe in surface provides a strong attractive potential for Hydrogen (not shown here) • Ab-initio process simulation combined with theoretical spectroscopy establishes a strong link between theory and experiment

45. Acid-basedcatalysis in zeolites Structure and nature of the catalytically active sites Surface-silanol groups (top-view) Structure of mordenite, looking down the main channel Si-Al-OH Bronsted sites in the main channel (a,b,d) and in the side-pocket (c)

46. Beckmann rearrangement • Transformation of oximes to amides: • Transition-state optimization • - maximize potential energy along one direction (reaction coordinate), • minimized with respect to all other degrees of freedom • - exact reaction coordinate is not known in advance • - basis set for ionic relaxation: internal coordinates (bonds, angles, • torsions,.... ) • - constrained relaxation – drag method: invert gradient corresponding • to estimated reaction coordinate • Calculation of reaction rate: Harmonic transition-state theory

47. Beckmann rearrangement • Conventional process • catalyzed by a sulfuric acid • problems with corrosion • large amount of by-products (ammonium sulfate, 4.0 t per t e-caprolactam) • Heterogeneously catalyzed reaction • environmentally friendly alternative to conventional process • catalyzed by solid acids such as zeolites • cyclohexanone oxime in the vapor phase – T~350C • problems short life-time of catalyst • what are the active centers?

48. BR catalyzed by Brønsted acid sites ΔEads=139.4 kJ/mol due to its size, cyclohexanone oxime can enter only into large pores (12 MR) ΔEads=53.9 kJ/mol

49. 1,2-H-shift Beckmann rearrangement at BA sites E (kJ/mol) 95.8 85.5 R_1 TS_1 R_2

50. N-insertion Beckmann rearrangement at BA sites 79.1 E (kJ/mol) 50.0 R_2 TS_2 R_3