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**Pseudopotentials and Basis Sets**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Pseudopotentials and Basis Sets How to generate and test them

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**Valence wave functions must be orthogonal to the core wave functions**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Pseudopotential idea Atomic Si Core electrons… highly localized very depth energy … are chemically inert 1s2 2s2 2p s2 3p2 Valence wave functions must be orthogonal to the core wave functions core valence

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**Shorter Rc: harder pseudo**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Cut-off radii Balance between softness and transferability controlled by Rc TRANSFERABILITY SOFTNESS Rc Si Larger Rc: softer pseudo Shorter Rc: harder pseudo

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**Valence configuration**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 The “atom” program “pseudopotential generation” label xc flavor # valence shells # core orbitals Valence configuration n l Cutoff radii

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**Procedure (I) Run the shell script (pg.sh)**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Procedure (I) Run the shell script (pg.sh) Check contents of new directory (Si.tm2) Plot the pseudo-potentials/orbitals

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**Logarithmic derivative**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Procedure (II) Logarithmic derivative Pseudo-wave function Radial Fourier-T Pseudopotential

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**Procedure (III) SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE**

University of Illinois at Urbana-Champaign, June 13-23, 2005 Procedure (III)

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**Radial charge distribution:**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Radial charge distribution: Compare all-electron with pseudo-charge

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**Pseudopotential testing (I)**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Pseudopotential testing (I) The all-electron (ae.sh) and pseudo-test (pt.sh) scripts: run script input pseudopotential to test

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**Pseudopotential testing (II)**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Pseudopotential testing (II) A transferable pseudo will reproduce the AE energy levels and wave functions in arbitrary environments

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**Pseudopotential testing (III)**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Pseudopotential testing (III) Compute the energy of two different configurations Compute the difference in energy For the pseudopotential to be transferible: 3s2 3p2 (reference) 3s2 3p1 3d1 3s1 3p3 3s1 3p2 3d1 3s0 3p3 3d1

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**Large core-valence overlap**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Large core-valence overlap Errors due to non-linearity of XC-potential

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**Non-linear core corrections**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Non-linear core corrections Standard pseudopotential unscreening: Valence charge only However… Core-correction Keep core charge in pseudopotential generation

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**SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE**

University of Illinois at Urbana-Champaign, June 13-23, 2005 PCC input file New flag

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**Pseudo-core & pseudo-valence charge**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Pseudo-core & pseudo-valence charge

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**Smooth Fourier Transform**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Smooth Fourier Transform The real-space grid required fineness depends on how you define the pseudopotential. The meshcutoff parameter can be determined from the Fourier Transform.

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**Basis generation SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE**

University of Illinois at Urbana-Champaign, June 13-23, 2005 Basis generation

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**Key for linear-scaling: LOCALITY**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Key for linear-scaling: LOCALITY Large system W. Yang, Phys. Rev. Lett. 66, 1438 (1992) “Divide and Conquer” x2

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**Atomic Orbitals Very efficient Lack of systematic for convergence**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Atomic Orbitals Numerical Atomic Orbitals (NAOs): Numerical solution of the KS Hamiltonian for the isolated pseudoatom with the same approximations (xc, pseudos) as for the condensed system Very efficient Lack of systematic for convergence Main features: Size or number of functions Range of localization of these functions Shape or functional form used.

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**SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE**

University of Illinois at Urbana-Champaign, June 13-23, 2005 Basis Size (I) Depends on the required accuracy and available computational power Quick and dirty calculations Minimal basis set (single-z; SZ) Highly converged calculations Complete multiple-z + Polarization Diffuse orbitals

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**Basis Size (II): improving**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Basis Size (II): improving Single- (minimal or SZ) One single radial function per angular momentum shell occupied in the free-atom. Improving the quality? Radial flexibilization: Add more than one radial function within the same angular momentum shell Multiple-ζ Angular flexibilization: Add shells of different angular momentum Polarization

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**Examples SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE**

University of Illinois at Urbana-Champaign, June 13-23, 2005 Examples

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**Basis Size (III): Polarization**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Basis Size (III): Polarization Perturbative polarization Atomic polarization Apply a small E field to the orbital we want to polarize Solve Schrödinger equation for higher angular momentum E s s+p unbound in the free atom require short cut offs Si 3d orbitals E. Artacho et al, Phys. Stat. Sol. (b), 215, 809 (1999)

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**Basis Size (IV): Convergence**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Basis Size (IV): Convergence Bulk Si PW and NAO convergence Cohesion curves J. Junquera et. al. PRB 64, (2001).

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**Range (I): How to get sparsity for O(n)**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Range (I): How to get sparsity for O(n) Neglecting interactions below a tolerance or beyond some scope of neighbours numerical instablilities for high tolerances. Strictly localized atomic orbitals (zero beyond a given cutoff radius, rc) Accuracy and computational efficiency depend on the range of the atomic orbitals. Way to define all the cutoff radii in a balanced way.

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**Range (II): Energy Shift**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Range (II): Energy Shift Easy approach to define the cutoff radii for the NAOs: A single parameter for all cutoff radii… E. Artacho et al. Phys. Stat. Solidi (b) 215, 809 (1999) Fireballs O. F. Sankey & D. J. Niklewski, Phys. Rev. B 40, 3979 (1989) …BUT, a different cutoff radius for each orbital

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**Range (II): Convergence**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Range (II): Convergence Bulk Si equal s, p orbitals radii J. Soler et al, J. Phys: Condens. Matter, 14, 2745 (2002)

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**Shape (I) dQ : extra charge per atomic specie.**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Shape (I) The radial function shape is mainly determined by the pseudopotential. Extra parameters can be introduced to add flexibility: dQ : extra charge per atomic specie. Confinement : imposed separately for each angular momentum shell.

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**(J. Junquera et al, Phys. Rev. B 64, 235111 (01) )**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Shape (II) Soft confinement (J. Junquera et al, Phys. Rev. B 64, (01) ) Shape of the optimal 3s orbital of Mg in MgO for different schemes Corresponding optimal confinement potential Better variational basis sets Removes the discontinuity of the derivative

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**PAO.Basis (I) 4s 3d # shells Add polarization**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 PAO.Basis (I) # shells Add polarization %block PAO.Basis # Define Basis set Cu 2 # Species label, number of l-shells n=4 0 2 P 1 # n, l, Nzeta, Polarization, NzetaPol 5.200 1.000 n=3 2 2 # n, l, Nzeta 3.541 1.000 %endblock PAO.Basis 4s 3d Rc 1st z 2nd z

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**PAO.Basis (II): new generation**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 PAO.Basis (II): new generation charge %block PAO.Basis # Define Basis set Cu 3 n=4 0 1 E n=4 1 1 E n=3 2 1 E %endblock PAO.Basis Vc rc Polarization orbital

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**Procedure Check the difference in energies involved in your problem**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Procedure Check the difference in energies involved in your problem For semiquantitative results and general trends use SZ Improve the basis: Automatic DZP (Split Valence & Perturbative Polarization): High quality for most systems Good valence between well converged results & computational cost ‘Standard’ Rule of thumb in Quantum Chemistry: « a basis should always be doubled before being polarized ». Functional optimization of the basis

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**Pseudos & Basis repository**

SUMMER SCHOOL ON COMPUTATIONAL MATERIALS SCIENCE University of Illinois at Urbana-Champaign, June 13-23, 2005 Pseudos & Basis repository Pseudopotentials and basis sets available in the SIESTA web page: Uploaded by users input files to generate them Plots of the radial functions Documentation of the tests done Author’s contact information The PAO is pseudopotential-dependent. Check also in the user’s mailing list.

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