LECTURE 11

DFT Supercell Calculations of Surfaces

W. F. Schneider    CBE 547 1
Fall Semester 2007
 Alkaline Earth Oxide Bulk Structures
2

experiment
-250

MgO
Bulk MgO LDA VASP
GGA VASP
• Rocksalt structure -300
LDA CPMD

ergy (eV)
Represent as -350
• Simple cubic unit cell

Ene
• 8 atom basis -400

• Optimize lattice constant

-450
3.5 4 4.5 5
lattice constant (Ang.)

Exp’t 4.212 Å
LDA Vasp 4.182
GGA Vasp 4.255
a LDA CPMD 4.240

W. F. Schneider    CBE 547 Fall Semester 2007
 Supercell Slab Models of Surfaces
3

(MgO bulk) (MgO slab)

Mg
g

O c

c
b
a
b
a

Selection off a surface

f model
• Surface cleavage plane

• “Thickness” of slab
Side view of 3 slab 
• Lateral cell dimensions images

• Size of vacuum spacing

Top view of 4 “2x2” unit cells

W. F. Schneider    CBE 547 Fall Semester 2007
 Miller Index Naming for Surface Planes
4

… Specify cleavage plane in integer lattice vector coordinates of a vector orthogonal to the plane
† Description thus depends on lattice vector choice
… Complete definition also must include vertical location of plane
… S f
Surface properties
ti highly
hi hl ddependent
d t on cleavage
l plane
l

(001) (013)

y
x

z
“Basal” plane
Supercell model of a stepped surface
y
(Lattice vectors become more messy to determine)
x
W. F. Schneider    CBE 547 Fall Semester 2007
 More Miller Planes
5

(111)

z y
x
Polar surface
Opposite faces have different compositions

Typically high energy and unstable to “reconstruction”

W. F. Schneider    CBE 547 Fall Semester 2007
 Supercell Dimensions
6

… Slab thickness typically a few “formula unit” layers

… Vacuum spacing large enough to isolate slab from periodic image
( 10 15 Å)
(~10-15
… Lateral dimensions based on need to isolate chemistry within a cell
… Always test toabe sure properties of interest are robust to model
2 atom

Nominally equivalent 
surface supercells
4 atom
8 atom Different effective 
separation between 
16 atom
16 atom neighbors
i hb

W. F. Schneider    CBE 547 Fall Semester 2007
 Surface Relaxation
7

… Exposed surfaces will often relax in response to loss of bonding at surface

… Typical to “freeze” one side of slab to simulate constraints of the bulk
… Ideally converge results with respect to slab thickness

0.01 Å 0.03 Å

0.01 Å
0.004 Å

4.212 Å
Fixed
MgO
0.02 J/m2 relaxation MgO (103) step relaxations

W. F. Schneider    CBE 547 Fall Semester 2007
 Surface Energy
8

(MgO bulk)
(MgO slab)
Eslab − nEbulk
γ= c
2A
c
b
a

… Energy cost to expose a surface by cleaving a bulk b

a
material
† Always a positive quantity
† Useful for valdiation, experimental comparison Distance between steps

… Comparison of energies between supercells of

different shapes, requires
† k-point convergence
† Energy cutoff convergence
† Equivalent computational parameters

… Slab k-points
† m×n×1
† m, n inversely proportional to lateral dimensions

W. F. Schneider    CBE 547 Fall Semester 2007
 Molecular mechanism of trapping on catalyzed oxides
9

CO, H2, HC
N2, CO2, H2O +
NO + ½ O2 NO2
NO2
SO2 + ½ O2 SO3

NO2 NO2

Pt SO3 O Pt SO3 O

O O

Trapping oxide (e.g. BaO) Trapping oxide (e.g. BaO)

Lean Conditions Rich Conditions

NOx and SOx oxidized & trapped NOx decomposed and reduced, SOx recalcitrant

… Key Questions:
† How does NOx get oxidized and adsorbed on a trapping material?
† How does the SOx chemistry compete with NOx?
† How can we select trap materials to optimize selectivity for NOx over SOx?

… This work: Compare SOx and NOx adsorption mechanisms on MgO(001)

W. F. Schneider    CBE 547 Fall Semester 2007
 Sulfur Oxides
10

SO2 ∠OSO = 106°
S
SO
S-O ∠OSO O2-
O
Exp’t 1.43 118.9
LDA 1.449 119.4

SO32-2

(sulfite)
½ O2

SO3 ∠OSO = 109.5

109 5°
O2-
S-O
Exp’t 1.42
LDA 1.439

SO42-
W. F. Schneider CBE 547 Fall Semester 2007 (sulfate)
 MgO (001) + SO2
11

1.502 1.505
1.47 1.655
1.536
117 0
117.0 2.132
2.17 1.755 2.062
2.211

2.448
Physisorbed SO2 Terrace chemisorbed SO2 Step chemisorbed SO2
-16 kcal mol-1 LDA -42 kcal mol-1 LDA -62 kcal mol-1 LDA

… Metastable dipolar physisorption

† Only structure found in cluster simulations
† Converts to chemisorbed at ~200 K in MD simulations (Ea ≈ 0.5 kcal mol-1)
… Strong “sulfite”-like chemisorption (MgO + SO2 Æ MgO·SO2)
† Specific S–Os and O–Mgs interactions; significant charge transfer to adsorbate
† Pronounced local lattice distortion, dies off over short range
… SO2 chemisorbs preferentially on coordinatively unsaturated edge ions
† Similar sulfite-like adsorption geometry
† SO2 oxygen fill vacant lattice sites
† Introduces pronounced lattice distortions along step edge
W. F. Schneider    CBE 547 Fall Semester 2007 11
 SO2 Chemisorption on MgO
12

BE, kcal mol-1

1 2 3 4 S O1 O2 LDA GGA
(100) -37 -25
1 (103) 4 1 3 -62 -46
1 1 3 -60
O 3 3 2 -59
59
1 1 2 -52
2 1 2 -46
S O 2 3 2 -34

(104) 4 1 3 -62

corner -92 -81

… Multiple SO2 chemisorption sites

† SO2 fills “virtual” lattice sites
† Adsorption
p energy
gy tracks with lattice ion coordinative
unsaturation
W. F. Schneider    CBE 547 Fall Semester 2007
 MgO + SO3
13

1.454
1.440 1.498
1.578
1.470

1.657 2.066
2.603

2.420 Å

MgO (001) + SO3 MgO (103) + SO3

-69 kcal mol-1 LDA -95 kcal mol-1 LDA
… “Sulfate”-like chemisorption (MgO + SO3 Æ MgO·SO3)
† Primary S–Os bonding → approximately tetrahedral SO4 structures
† Large, local relaxation of Os, charge transfer to SO3
† Secondary O–Ms interactions fix orientation
… 30 kcal mol-1 greater than SO2
Chemisorption energy ~30
† Strong preference for coordinatively unsaturated ions
W. F. Schneider    CBE 547 Fall Semester 2007
 MgO + SOx Vibrational Spectroscopy
14

W. F. Schneider    CBE 547 Fall Semester 2007
 NO•/NO2• Physisorption on MgO Terrace
15

Physisorbed NO Physisorbed NO2

-0.19 e 128º 1.24 -0.26 e
1.19 -0.23 e
1 24
1.24 125º
110º
2.27 2.25
2.25

MgO(001) + NO MgO(001) +NO2 N-down MgO(001) +NO2 O-down

-7 kcal mol-1 -4 kcal mol-1 -10 kcal mol-1

… NO and NO2 physisorb on MgO terraces

† Low NOx Lewis basicity produces long, weak adsorbate-surface bonds
† Charge-dipole interaction, limited charge transfer to adsorbate
… Not consistent with observations of “nitrite” and “nitrate” upon exposure of
MgO
g to NOx!

W. F. Schneider    CBE 547 Fall Semester 2007
16

W. F. Schneider    CBE 547 Fall Semester 2007
 Cooperative NO2 Adsorption on MgO(001)
17

e- “nitrite”
“nitrate” NO2- + Mgs2+
NO2+ + Os2- 1.28 1.28
-0 23 e
0.23 -0 73 e
0.73
-0.26 e -0.78 e
1.22 117

1.41 2.09 2.11

-1.22 e 2.32

Isolated physisorbed NO2 -15 kcal mol-1

… Charge transfer generates cooperatively adsorbed NO2 pair

† Structural modifications consistent with chemisorption
† Mulliken populations reflect redistribution of charge between adsorbates
† Binding energy enhanced by 15 kcal mol-1 (100%) over two isolated NO2!
… Mixed nitrite/nitrate consistent with experimental observation for NO2-exposed
M
MgO

W. F. Schneider    CBE 547 Fall Semester 2007
 Distance Dependence of Cooperative Chemisorption
18

Unique “Lewis Acidic”

“Lewis Basic”
NO2 Sites
NO2

Mg O Mg O Mg O 35
30

nergy
O Mg O Mg O Mg
25

Total Adsorption en
(kcal/mol)
Mg O Mg O Mg O 20
15
O Mg OA Mg O Mg
10

Mg OC Mg OB Mg O
5
0
OF Mg OD Mg OE Mg A B C D E F oo
Adsorption site
“3x3” MgO supercell

… Cooperative effect decreases slowly with adsorbate separation

† e- transfer/pairing
/p g can occur over several Angstroms
g
† Forced charge separation yields physisorption

W. F. Schneider    CBE 547 Fall Semester 2007
 Bulk and Surface Structures of FCC Metals
19

Bulk FCC Pt
3 -5.5

2.95 Lattice Constant -5.6

Å)

Total energy
attice Constant (Å

2.9 -5.7

2.85 -5.8

2.8 -5.9

2.75 -6

2.7 -6.1
La

2.65 -6.2

2.6 -6.3
aa
2.55 a -6.4

2.5 -6.5
0 50 100 150 200
k points
k-points

Theory Expt’
Lattice Constant
3.986 3.923
(Å)
Surface energy
1.48 --
(J/m2)

W. F. Schneider    CBE 547 Fall Semester 2007
 FCC (111) Surface Supercell Models
20
3 Pt × 3 Pt 4 Pt × 4 Pt

a 8.453 Å 11.271 Å

20.921 Å
1×1

2×2

1×2 √3×√3

Æ
c
Æ
b Æ
a
(a) -120

mol-1)
4×4 N
-100 O

Adsorption Energy (kcal

-80

-60
NO
-40
NO2
-20
A

0
3 layer 4 layer 5 layer
W. F. Schneider    CBE 547 Fall Semester 2007
 Adsorption Sites on FCC (111) Surfaces
21

Adsorption sites on the (111) facet:

fcc – 3-fold hcp – 3-fold

coordination coordination

atop – 1
1-fold
fold bridge – 2-fold
coordination coordination

Hexagonal arrays of sites

o DFT calculations performed with Vasp
o 3×3, 4×4, 5×5 Pt(111) supercell models
o 8×8×1, 6×6×1, and 4×4×1 Monkhorst‐Pack k‐point grids
o “PAW” electron core treatment
o PW91 generalized gradient approximation
91 li d di i i

W. F. Schneider    CBE 547 Fall Semester 2007
 Oxygen adsorption and interactions on Pt(111)
22

Low coverage (1/16 ML) O preference for FCC adsorption

Pt(111) +
½ O2 < < <

fcc: -1.29 eV hcp: -0.89 eV fcc-hcp bridge (TS) atop: +0.18 eV

Lateral interaction effects on O adsorption (4 x 4 supercell)

2.4 Å

fcc-fcc: 1NN fcc-fcc: 2NN fcc-fcc: 3NN fcc-hcp: 1NN fcc-hcp: 2NN
+0 20 eV
+0.20 +0 10 eV
+0.10 +0 01 eV
+0.01 +0 82 eV
+0.82 +0 32 eV
+0.32

W. F. Schneider    CBE 547 Fall Semester 2007
 Characterizing Pt(111)-O Surface Coverage

O atom
+ Pt atom
… Adsorbates
interact with each Clean Pt(111) surface p(1 × 1)—O ordering
other to produce
different stable 80
configurations at Atop only
different 60 HCP onlyy
Mixed
coverages 40
Eforrm (meV Å‐2)

20
0
-20
-40
-60
0.000 0.125 0.250 0.375 0.500 0.625 0.750 0.875 1.000
O Coverage (ML)

ACS ‐ 21 August 2007 W. F. Schneider

 Surface free energies
Canonical ensemble Grand canonical ensemble
Helmholtz free energy Transformed Helmholtz energy
Constant atom number Constant oxygen potential

F (T , V , N O ) = E − TS F (1) (T ,V , μO ) = E − TS − N O μO

(1)
Fsurf − Fbulk
(1)
Fθ(1) − FPt(111)
(1)

Δγ θ =
(1)

γ Pt (111) =
(1)

A A

Bulk Pt Pt(111) Pt(111)‐θ(O)

ΔE (T , V ) = ESurf
DFT
− EBulk
DFT ΔE (θ , T , V ) = EθDFT − EPtDFT
(111)

+ ESurf
ZP
− EBulk
ZP + EθZP − EPtZP(111)
+ EθVib (T , V ) − EPtVib(111) (T ,V )
f ( T , V ) − EBulk ( T , V )
+ ESurf
Vib Vib

ΔS (T , V ) = S Surf
Vib
(T ,V ) − S Bulk
Vib
(T ,V ) ΔS (θ , T , V ) = SθVib (T , V ) − SPt(111)
Vib
(T , V )
Supercell calculations on thick slabs 4‐layer supercells
Phonon calculations for bulk and surface
Phonon calculations for bulk and surface O atom vibrations
O atom vibrations
Einstein vibrational model Einstein vibrational model

W. F. Schneider ACS ‐ 21 August 2007

 Pt(111)/O2 Phase Diagram
O2 (T,P) 1 ⎛ DFT ⎛ PO2 ⎞ ⎞
μO = ⎜⎜ EO2 + EO2 + ΔGO2 (T ) + k BT ln ⎜
ZP D
⎟ ⎟⎟
c 2⎝ ⎝ 1 bar ⎠⎠
O O O O

Pt(111) surface
O2 (g) + 2* 2O*
… O coverage
g limited byy accessible O2 T 1200 1200

and P O atom
1100
clean surface
… XPS performed to determine O Pt atom
coverage at various O2 exposures 1000 1000

Temperaturre (K)
900
† Ribeiro et al. p(4×4)–O
… Wellll kknown llow-pressure θ = 0.25
W 0 25 800800
p(2×4)–O
(2 4) O
coverage used to calibrate XPS 700
c(4×4)–3O
† Consistent with p(2×2)-O ordering p(2×2)–O θ = 0.39
… High-pressure θ = 0.5 coverage 600600
θ = 0.40
consistent with p(2×1)-O ordering 500
θ = 0.52
Likely highest coverage accessible with θ = 0.25 θ = 0.49
†
O2 at ambient conditions
400400

300 c(2×4)–3O θ = 0.48

… Kinetics limit rate of O2 loss from c(4×4)–7O p(2×1)–O
surface 200200
-13 -11 -9 -7 -5 -3 -1 1

-13
13 -11
11 -9
9 -7
7 -5
5 -3
3 -1
1 1
log10(PO2/1 bar)

ACS ‐ 21 August 2007 W. F. Schneider

 Coverage-dependent O binding energies
2
¼ ML ½ ML dE form
BEOxygen ∝
V/O)

1.5
dθ
ng energy (eV

+ NO →
NO → + NO
NO2
1
ΔE2 (θ)
p(2×1)‐O
0.5 Apparent 
NO + O* → NO2 window of 
½ O2 → O* p(√3×√3)‐2O
favorable ΔE1
favorable ΔE
Oxxygen bindin

0
and ΔE2
-0.5
+ ½ O2 →
-1
ΔE1 (θ)
-1.5
0 0.2 0.4 0.6 0.8 1

Oxygen coverage (ML)
… S f
Surface exhibits
hibit att lleastt ttwo di
distinct
ti t bi
binding
di energy regimes
i
† Low coverage BE in middle of experimentally available values
… O2 dissociation exothermic only up to a limiting coverage near θ = 2/3
… NO oxidation exothermic only at coverages above about θ = ½
† Based on experimental NO oxidation energy

ACS ‐ 21 August 2007 W. F. Schneider

 O2 adsorption on Pt(111)-O(X)
• TBT and TFB isomers  θO = 0 θO = 0.25 θO = 0.5
energetically 
equivalent

• Exothermically bound 
at low θO

• Adsorption energy  ΔE = ‐0.80 eV ΔE = ‐0.23 eV ΔE = +0.57 eV

diminishes greatly 
with coverage
– Strong electrostatic 
repulsion
li

• Endothermically
bound at catalytic 
coverage
g ΔE = ‐1.56 eV ΔE = ‐1.03 eV ΔE = ‐0.41 eV
– O2* unlikely precursor to 
dissociation

• How does O2
participate in the 
reaction??
ti ??

ACS ‐ 21 August 2007 W. F. Schneider

 O2 dissociation on Pt(111)-O(X)
28

a) O2 (g) + 2* → 2O*
… “Nudged
elastic
l b
band”
d”
(NEB)
calculations of 3
reaction 2.14 eV
pathways
h 2
ergy (eV)

… Reaction 1

barrier O2 (g) -0.05 eV

0
depends on
Ene

-1
surface
coverage -2 TSOtrans
2 (g)

-3

p(2×1)-O
p( ) Pt(111)
( )

W. F. Schneider    CBE 547 Fall Semester 2007