assessment of dft methods for solids · 3 mssc2009 - september, 10th 2009 - raffaella demichelis -...
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ASSESSMENT OF DFT METHODSASSESSMENT OF DFT METHODSFOR SOLIDSFOR SOLIDS
Università di TorinoDipartimento di Chimica IFM
MSSC2009 - Ab Initio Modeling in Solid State Chemistry
Raffaella Demichelis
MSSC2009 - September, 10th 2009
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Table of Contents
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT: a quick overview
PBE’s type functionals
Hybrid GGA functionals
DFT & CRYSTAL
CRYSTAL input for DFT calculation
DFT functionals available in CRYSTAL
Integration grid and numerical accuracy control
Performance of DFT functionals for describing periodic systems quasi-1D systems: SWCNTs and Chrysotile
Aluminosilicates
Relative stability of polymorphs
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT energy
The Jacob’s Ladder(Perdew, Schmidt; AIP Conf. Proc. 2001, 577, 1-20)
LDAGGA
meta-GGA Exact exchange, compatible correlation
DFT: a quick overview
Hohenberg, Kohn; Phys. Rev. 1964, 136, 864Kohn, Sham, Phys. Rev. 1965, 140, 1133
DFT HEAVEN
E=E[ρ(r)]=Enuclear+Ekinetic+Enucl-electron+Ecoulomb+EXC
Exact exchange, exact partial correlation
HARTREE WORLD
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT: a quick overview
PBE’s type exchange functionals
EX= !"#X ," [!" ]$
"% F(s" [!" ,&!" ])dr
Spin density
Reduced spin density
Exchange energy density
Different forms of F(sσ) were proposed:
PBE (1996) WC* (2006)revPBE (1998) PBEsol* (2008)RPBE (1999) SOGGA* (2008) [1/2 PBE+ 1/2 RPBE]mPBE (2002) *CRYSTAL09
(B. Civalleri - 2008)
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT: a quick overview
HF/DFT hybrid functionals
EXC=a*[EX(HF)-EX(DFT)] + EXC(DFT) (e.g. PBE0)
a=fraction of exact exchange
EX=(1-a)*[EX(LDA)+b*EX(XXX)]+a*EX(HF) EC=(1-c)*EC(VWN)+c*EC(YYY)
(XXX, YYY: non-local exchange and correlation)
(e.g. B3LYP: XXX=B, YYY=LYP B3PW: XXX=B, YYY=PW91)
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Use of hybrid functionals in solid state simulation
*a matter of discussion in the scientific community•claimed lacks in accuracy•use of empirical parameters•bad description of narrow-gap and conducting systems•…
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT: a quick overview
HF/DFT hybrid functionals
*largely diffuse (e.g. B3LYP, B3PW, PBE0) and often provedto provide the best results for structural, electronic, thermodynamical and dynamical properties of non-conducting systems (in particular H-containing systems)
F. Corà, M. Alfredsson, G. Mallia, D.S. Middlemiss, W.C. Mackrodt, R. Dovesi, R. Orlando, Volume 113, 171-232.Springer-Verlag, Heidelberg (2004).
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT: a quick overview
HF/DFT hybrid functionalsThe example of Brucite, Mg(OH)2
Differences between calculated and experimental results:a,c: lattice parameters, Å ΔV%: volumes, relative difference (calc-exp)/exp*100OH: bond length of OH group, Å v: anharmonic stretching of the OH oscillator, cm-1
Hybrids
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT: a quick overview
HF/DFT hybrid functionals
SVWNPBEB3LYPPBE0HFExp. -3.65
J/K
KMnF3 exchange coupling constant
(J in Kelvin)Calculated by A. Meyer,
CRYSTAL06, 2009
pyrope grossular andradite spessartine uvaroviteSVWN PBEB3LYPPBE0HFExp. 3.06 2.96 3.53 3.24 3.42
Calculated vs experimental dielectric constants ofgarnets. No experimental data for almandine
Open-shellClosed-shell
A. Meyer, M. Ferrero, L. Valenzano, C. M. Zicovich-Wilson, R. Orlando, R. DovesiIn preparation
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
CRYSTAL input for DFT calculation
title1 - GEOMETRY block2 - BASIS SET block3 - HAMILTONIAN and SCF block
Structure ofCRYSTAL input
DFToptionsEND
Options:1 - Choice of the exchange-correlation functionals2 - Integration grid and numerical accuracy control3 - Atomic parameters(and add SPIN for open-shell systems)
DFT input block
In block 3:
For points 2-3 default values are suppliedPoint 1 must be set
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
DFT functionals available in CRYSTAL
EXCHANGE CORRELATION
LDA LDA (=S) PWLSDVWNPZ
VBH VBH
GGA BECKE LYPPWGGA (=PW91) PWGGA (=PW91)PBE PBEPBESOL* PBESOL*WCGGA* (=WC) P86SOGGA* WL
(References in the CRYSTAL users’ manual)*CRYSTAL09
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CRYSTAL input for DFT calculation
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
DFTEXCHANGE……..CORRELAT……..
If not set, EX(HF) used
If not set, no EC
Percentage of EX(HF), if notset: pure DFT
Non-local weightingparameters for EC
HYBRID…NONLOCAL… …
1 - Choice of the functional
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
GLOBAL KEYWORDS EXCHANGE CORRELAT HYBRID NONLOCAL
SOGGAXC* SOGGA PBE - -
PBE1PBE* PBE PBE 25 -(PBE0)
B3PW BECKE PWGGA 20 0.9 0.81
B3LYP BECKE LYP 20 0.9 0.81
(References in the CRYSTAL users’ manual)
CRYSTAL input for DFT calculation
1 - Choice of the functional
*CRYSTAL09
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
Integration grid and numerical accuracy control
EXC and its gradient are evaluated by numerical integration over the cell volume: an integration grid is required
- Grid based on atomic partition method (Becke), Vcell partitioned into atomic volumes: VA centered on atom A
- Radial and angular components (Gauss-Legendre radial quadrature, Lebedev 2-dimensional angular point distribution;
points associated to a weight, w)Uniform (or unpruned) grid
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
Integration grid and numerical accuracy control
For reducing the grid size and maintaining its effectiveness:
pruned grid (not radially uniform):
the number of angular points is maximum in the valence regionand gradually decreases in both directions
Mg
O
O
O
O
Radial points: Gauss’ formula(nr=number of radial points)
Angular points: Lebedev distribution(L=Lebedev accuracy parameter)
001 plane of a unit cell of MgO
Grid of Mg
Grid of O
The example of MgO(R. Orlando - 2006)
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
Integration grid and numerical accuracy control
Integration grid and numerical accuracy control
unpruned grid pruned grid
nr=55 L=13
nr=75 L=13
nr=75 L=16
-275.43121602 (31878)
-275.43123518 (42956)
-275.43127155 (96038)
-275.43123079 (11552)
-275.43123451 (20542)
-275.43127167 (41530)(R. Orlando - 2006)
DFT & CRYSTAL
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
size of grid
telapsed (s)
20542
7.27
41530
14.13
11552
4.41
55, 13 75, 13 75, 16
41530
1437
14.13
1.56
20542
882
7.27
0.86
11552
513
4.41
0.42MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
Integration grid and numerical accuracy control: use of symmetry
(R. Orlando- 2006)
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CRYSTAL input for DFT calculation
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
RADIAL… … …ANGULAR… … …
2 - Integration grid and numerical accuracy control
Number of intervals, integration interval limits,number of radial points in the ith interval, nr
Number of intervals, integration interval limits,accuracy level (L) of each integral
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CRYSTAL input for DFT calculation
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
RADIAL14.055ANGULAR100.4 0.6 0.8 0.9 1.1 2.3 2.4 2.6 2.8 9999.01 2 5 8 11 13 11 8 5 1
Angular points generated(38 50 110 194 302 434 302 194 110 38)
Default grid: (55,434)p -- 434 angular points in the valence region
2 - Integration grid and numerical accuracy control
L
nr
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CRYSTAL input for DFT calculation
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
GLOBAL KEYWORDS:LGRID --> nr=75, L=13; (75,434)pXLGRID --> nr=75, L=16; (75,974)p
XXLGRID --> nr=99, L=18; (99,1454)p(see CRYSTAL users’ manual for details)
Numerically integrated density (NID)Diaspore, 4AlOOH in the unit cell, 120 electrons
Grid NID ΔDEFAULT 119.998710 1.3E-03 XLGRID 120.000054 -5.4E-05XXLGRID 119.999986 1.4E-05(nr=99,L=22) 119.999999 1.0E-06
2 - Integration grid and numerical accuracy control
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CRYSTAL input for DFT calculation
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
2 - Integration grid and numerical accuracy control
default LGRID XLGRID 75,16 unpr 75,18 unpr
18 (IR+Raman+silent)Average of Abs diff.Maximum differenceMinimum differenceGrid pointsµ-electron (TOT: 100 e)µ-hartreeÅÅ
Calcite: effect of the grid on geometry and vibrational modes
M. Prencipe, F. Pascale, C. M. Zicovich-Wilson, V. R. Saunders, R. Orlando, R. Dovesi; Phys. Chem. Miner.,2004, 31, 559-564
0 Reference00
0
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CRYSTAL input for DFT calculation
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
2 - Integration grid and numerical accuracy control
55,434 77’870 0.9621 382275,434 106’210 0.9623 3843 (LGRID) 49’894 0.0002 -0.899,434 140’038 0.9622 384255,974 174’066 0.9619 382475,974 237’164 0.9619 3846 (XLGRID) 100’554 0.0001 -1.499,974 311’570 0.9619 384499,1454 463’462 0.9619 3844
nr,L N. points O-H ν(OH)h Pruned Np O-H ν(OH)h
(uniform)
OH vibrational data of brucite:Effect of pruned and unpruned grid size
S. Tosoni, F. Pascale, P. Ugliengo, R. Orlando, V. R. Saunders, R. Dovesi; Mol. Phys., 2005, 103, 2549-2558
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CRYSTAL input for DFT calculation
MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
2 - Integration grid and numerical accuracy control
Details on the grid size and its performance:
M. Prencipe, F. Pascale, C. M. Zicovich-Wilson, V. R. Saunders, R. Orlando,R. Dovesi; Phys. Chem. Miner., 2004, 31, 559-564
F. Pascale, C. M. Zicovich-Wilson, R. Orlando, C. Roetti, P. Ugliengo, R.Dovesi; J. Phys. Chem. B, 2005, 109, 6146-6152
S. Tosoni, F. Pascale, P. Ugliengo, R. Orlando, V. R. Saunders, R. Dovesi;Mol. Phys., 2005, 103, 2549-2558
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
DFT & CRYSTAL
CRYSTAL input for DFT calculation
2 - Integration grid and numerical accuracy control- unpruned grid can be set- thresholds on grid weigths and electronic density can be increased ordecreased with respect to default- different methods for the point weights- keywords for memory menagement
3 - Atomic parameters - set atomic radius and formal charge different fromthe computed one
(see CRYSTAL users’ manual for details)
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
Performance of DFT functionals for describing periodic systems
TEST SYSTEMS:
+ SW-carbon nanotubes+ SW-chrysotile
+ aluminium hydroxides semi-ionic, H-containing, HBs, layered and non-layered
+ brucite semi-ionic, H-containing, no HBs, layered+ orthosilicates semi-ionic, H-free+ garnets “ “+ olivine “ “+ Si and Al oxides “ “(+ diamond, silicon pure-covalent, “) work in progress(+ MgO pure-ionic, “) work in progress
quasi-1D
3D
POSTER N. 4R. Demichelis, B. Civalleri,Y. Noel and R. Dovesi
TEST FUNCTIONALS: SWVN, SPWLSD (LDA)PBE, PW91, PBEsol,WC-PBE,SOGGA-PBE (GGA)B1WC, WC1LYP, B3PW, B3LYP, PBE0 (hybrids)
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
Performance of DFT functionals for describing periodic systems
SWCNTs: all the tested DFT functionals (LDA, GGA, hybrids)provide reasonable results for structure, energetics andvibrational frequencies. The choice of Hamiltonian iscrucial for the description of the band gap.
Chrysotile: comparison PBE0 vs B3LYP. Both provide good structures and relative stability. PBE0 structural data arehowever more accurate.
Quasi-1D systems
P. D'Arco, Y. Noel, R. Demichelis, R. Dovesi (2009) J. Chem. Phys., accepted
R. Demichelis, Y. Noel, P. D'Arco, R. Dovesi (2009) in preparation.
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
Performance of DFT functionals for describing periodic systems
Aluminosilicates
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
Performance of DFT functionals for describing periodic systems
Aluminosilicates
ΔV%
1- R. Demichelis, B. Civalleri, MFerrabone and R. Dovesi;Int. J. Quantum Chem. (2009)DOI: 10.1002/qua.22301
2- R. Demichelis, B. Civalleri, P.DʼArco, R. Dovesi; (2009) inpreparation
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
Performance of DFT functionals for describing periodic systems
The relative stability of the polymorphs
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MSSC2009 - September, 10th 2009 - Raffaella Demichelis - Assessment of DFT methods for solids
Performance of DFT functionals for describing periodic systems
In general:
+
++
1- R. Demichelis, B. Civalleri, P. DʼArco, R. Dovesi; (2009) in preparation
+
2- L. Valenzano, M. Ferrabone, B. Civalleri, R. Dovesi; (2009) in preparation
The relative stability of the polymorphs