glass structure and first-principles nmrjry20/gipaw/inorg_app.pdf · introduction nmr of...

Introduction NMR of Borosilicate Glasses First-Principles NMR

Glass Structure and First-Principles NMR

Thibault Charpentier

CEA / IRAMIS / SIS2M / LSDRM

CECAM Tutorial - September 2009

Thibault Charpentier CEA / IRAMIS / SIS2M / LSDRM

First Principles NMR of Glass - CECAM Tutorial 2009


Glass: a Nuclear Waste Storage MaterialLong term behavior studies: structure and alteration



R7T7 & SON68 GlassesA complex borosilicate glass comprising more than 30 oxides

oxide % (w)

29SiO2 45.1227Al2O3 4.8711B2O3 13.926,7Li2O 1.9723Na2O 9.7843CaO 4.01ZrO2 0.99

ZnO 2.48Fe2O3 2.89P2O5 0.28NiO 0.41Cr2O3 0.50Fission Products 10.35Actinides 0.89Platinoides 1.54

For Solid State NMR studies:Simplified Composition

3-8 oxidesNMR Probes

11B 27Al 29Si 23Na 43Ca 6,7Li 17O


NMR Structural studiesProbing the glass structure at the atomic scale

éléments de base de la matrice vitreuse : SiO2, Na2O, B2O3, Al2O3

Incorporation de produits de fission PF sous forme d’oxydes (PF2O3…)

Na

O

SiB Al

PF

Na

O

SiB Al

éléments de base de la matrice vitreuse : SiO2, Na2O, B2O3, Al2O3


Na

O

SiB Al

PF

Na

O

SiB Al


Na

O

SiB Al Na

O

SiB Al

PF

Na

O

SiB Al Na

O

SiB Al

Incorporation of fission product

Vitreous matrix structure

Glass accommodates the elements present in the spent fuel

FP atoms are an integral part of the glass




Solid State Nuclear Magnetic Resonance SpectroscopyBoron speciation in borosilicate glass

Identifying the structural units of the

glass network

-100102011B δ / ppm

[4]B

[3]B

[3]B

[4]B

"Resolved" Spectrum

O

B

MAS @ B0= 11.75 T

-100102011B δ / ppm

MAS @ B0 = 18.8 T

High Field MAS NMR:

Boron speciation resolved




Solid State Nuclear Magnetic Resonance SpectroscopyHeavy Ion Damage: amorphisation of amorphous material ?

-20-10010203011B chemical shift (ppm)

PristineIrradiated

BO4-

BO3

Coll. CEA/DEN/DTCD S. Peuget, J.M. Delaye




Oxygen Speciation in borosilicate glassReading the silicate network structure

-100-5005010015017O δ / ppm

MAS @ B0= 11.75 T

MAS Unresolved

-60-40-2002040608010012017O δMAS / ppm

-70

-60

-50

-40

-30

-20

-10

17O

δIS

O /

ppm

Si-O -Na +

Si-O -[Na +,Ca ++

]B-O-B

Si-O-B

Si-O-Si

MQMAS @ B0= 11.75 T

2D technique required: MQMAS




Oxygen Speciation in borosilicate glassReading the silicate network structure

-100-5005010015017O δ / ppm

MAS @ B0= 11.75 T

MAS Unresolved

-60-40-2002040608010012017O δMAS / ppm

-70

-60

-50

-40

-30

-20

-1017

O δ

ISO

/ pp

m

Si-O -Na +

Si-O -[Na +,Ca ++

]B-O-B

Si-O-B

Si-O-Si

MQMAS @ B0= 11.75 T

2D technique required: MQMAS




Modeling and Quantifying 17O MQMAS SpectroscopyQuantification & NMR Distribution F. Angeli, T. Charpentier et al. JNCS 2008

-40-200204060

-50

-40

-30

-20

-10

0

δ ISO /

ppm

Experiment

17O MQMAS @ 11.75 T

-60-50-40-30-20-100ISOTROPIC dimension (ppm)

-40-200204060δMAS / ppm

-50

-40

-30

-20

-10

0

δ ISO /

ppm

Simulation

MQMAS Efficiency Profile

0 2 4 6 8 1017O CQ / MHz (η=0.5)

0

0,1

0,2

0,3

0,4

sign

al S

(CQ) /

arb

. uni

t

MQMAS Exp.

MQMAS Sim.

ISO. proj. Fit

SiOSi (72%)SiONa (28%)

SiOSi

SiO-Na+

SiONa CQ=2.0 MHz δiso= 32 ppm

SiONa CQ=4.7 MHz δiso= 48 ppm

Uncorrelated model of NMR parameter distributionp(CQ , η, δiso) = G (CQ)× G (η)× G (δiso)




Oxygen Speciation in borosilicate glassReading the silicate network structure F. Angeli, T. Charpentier et al., JNCS 2008

-60-40-2002040608010012017O δMAS / ppm

-70

-60

-50

-40

-30

-20

-10

17O

δIS

O /

ppm

Si-O -Na +

Si-O -[Na +,Ca ++

]

B-O-B

Si-O-B

Si-O-Si

MQMAS @ B0= 11.75 T

-60-40-2002040608010012017O δMAS / ppm

-70

-60

-50

-40

-30

-20

-1017

O δ

ISO

/ pp

m

Si-O -Na +

Si-O -[Na +,Ca ++]

B-O-B

Si-O-B

Si-O-Si

MQMAS @ B0= 11.75 T

Total Simulation of MQMAS spectroscopy




Oxygen Speciation in borosilicate glassQuantifying the glass network structure

-100-5005010015017O δ / ppm

Si-O-Si

Si-O-B

B-O-B

Si-O-Na+,Ca++ Si-O-Na+

ExperimentSimulation

MAS @ B0= 11.75 TGlass Topology

Bridging Oxygen Atoms:Si-O-Si, Si-O-B, B-O-BGlass homogeneity at nanoscale

Non Bridging Oxygen: Si-O−Na+

Glass Polymerization degree

Non Bridging Oxygen:Si-O−(Na+,Ca++)

Evidence of a Mixed Alkali -

Alkaline Earth Effect




Quantifying glass topological disorder

1 2 3 4 5 6 717O Quadrupolar Coupling Constant CQ / MHz

0

20

40

60

80

100

120

17O

Isot

ropi

c C

hem

ical

shi

ft δ is

o / pp

m

Si-O-SiSi-O-B

B-O-B

Si-O-Na+

Si-O-Na+,Ca++

MQMAS @ B0= 11.75 T

Glass Topology

Reconstruction of the NMRparameter distribution Π

Correlating the local disorder to theNMR spectrum line shape ?

Π(NMR) ⇒ Π(Structure) ?




NMR of disordered MaterialsModeling and Interpreting




Understanding NMR / Structure relationshipsQuantum Mechanical calculations: the Cluster Approach

Si(OH)3-O-Si(OH)3

120 130 140 150 160 170 1804

5

6

7

17O

Qua

d. C

onst

ant C

Q /

MH

z

1,5 1,6 1,7 1,84

5

6

7

120 130 140 150 160 170 180Si-O-Si angle (degree)

0

0,2

0,4

0,6

0,8

117

O η

Qua

d. A

sym

met

ry

1,5 1,6 1,7 1,8Si-O distance (angstroem)

0

0,2

0,4

0,6

0,8

1

η(Si-O-Si)

CQ(Si-O-Si) CQ(Si-O)

η(Si-O)

17O CQ and ηQ NMR parameters are allmost exclusively controlled by

local properties: (Si-O-Si bond angle and Si-O bond length)




Combining MD simulations with fp NMR calculationsGIPAW: C.J. Pickard & F. Mauri, PRB 2001




The GIPAW methodGauge Including Projector Augmented Wave C.J. Pickard & F. Mauri, PRB 2001

DFT using GGA (PBE) or LDAfunctionals.

Plane Waves Expansion (e−ik.r)

3D FFT, Parallel CodePeriodic Boundary Conditions

Pseudopotential approximation ofcore electrons

GI-PAW

PAW: Reconstruction of thewave function at the nucleusGI: Gauge Invariance

-100 -50 0 5017O δ / ppm

-200 0 20017O δ / ppm

Experiment

α-cristobalite SiO2

GIPAW

Exp.: Spearing et al. Phys. Chem. Minerals 1992.

STATIC MAS

Accuracy: GIPAW outperforms all previous approaches




Molecular DynamicsMD-GIPAW Methodology

0 200 400 500 510 520 530Time (ps)

0

1000

2000

3000

4000

Tem

pera

ture

(K)

NMR

Molecular Dynamics : Classical + Ab Initiosupercell ~ 100 - 1000 atoms

Quench

1012-15K/s

Liquid

Relaxation

ab initio MD Car-ParinelloClassical MD

0K

Vij+ (Vijk) E0[ρ(r)]

0 20 40 50 60 70 80Time (ps)

0

1000

2000

3000

4000

Tem

pera

ture

(K)

NMR

Molecular Dynamics : Full Ab Initiosupercell ~ 100 atoms

Quench

1012-15K/s

Liquid

Relaxation

ab initio MD Car-Parinello

0K

E0[ρ(r)]

MD: Collaboration S. Ispas, P. Kroll, G. Ferlat, F. Mauri, J.M. Delaye




The controversy: Bond Angle Distribution in vitreous silicaRevisiting the interpretation of 17O NMR data




A Monte Carlo / MD Hybrid ApproachModeling Glass Structure: Bond Switching Algorithm

0 200 400 500 510 520 530Time (ps)

0

1000

2000

3000

4000

Tem

pera

ture

(K)

NMR

Molecular Dynamics : Monte Carlo + Ab Initiosupercell ~ 100 - 1000 atoms

Relaxation

ab initio MD Car-Parinello

Random Network Generation

0K

Bond Switching Algorithm

E0[ρ(r)]

V = α (∆rij)2+β(∆Θijk)

2

Defect Free Vitreous SilicaContinuous Random Network




Simulation of NMR SpectraThe simple approach

3 4 5 6 717O CQ / MHz

20

30

40

50

60

70

17O

δis

o / pp

m

I (~ν) =∑

i

I ith (~ν)




Simulation of NMR SpectraThe simple approach

-120-80-400408017O δMAS / ppm

-60

-40

-20

0

20

40

17O

δIS

O /

ppm

DAS @ 9.4 T

-120-80-400408017O δMAS / ppm

-60

-40

-20

0

20

4017

O δ

ISO /

ppm

DAS @ 9.4 T

Experiment

Clark et al. PRB 2004




Simulation of NMR SpectraKernel Density Estimate Approach

3 4 5 6 717O CQ / MHz

20

30

40

50

60

70

17O

δis

o / pp

m

CQ , η, δisoi ⇒ p (CQ , η, δiso)

Kernel: p(x) =∑

i

KHi(x− xi)

I (~ν) =

∫p (CQ , η, δiso)

× Ith (~ν;CQ , η, δiso)




Simulation of NMR SpectraKernel Density Estimate Approach

-120-80-400408017O δMAS / ppm

-60

-40

-20

0

20

40

17O

δIS

O /

ppm

DAS @ 9.4 T

-120-80-400408017O δMAS / ppm

-60

-40

-20

0

20

40

17O

δIS

O /

ppm

DAS @ 9.4 T

Experiment





Glass TopologyThe (small)-rings statistics

Local structure 17O NMR parametersRing Size SiOSi CQ η δiso

degrees MHz ppm3 126.7 (4.1) 4.61 (0.35) 0.38 (0.15) 55.92 (7.85)4 142.3 (10.9) 5.03 (0.39) 0.24 (0.13) 46.54 (6.42)

> 4 147.0 (12.2) 5.21 (0.41) 0.20 (0.12) 39.59 (6.55)

Experiment(a) 5.08 (0.37) 0.15 (0.04) 36.7 (4.3)(a) Clark et al. PRB 2004

Local structure 29Si NMR parametersRing Size SiOSi δiso Ωσ κσ

degrees ppm ppm3 135.4 (12.4) -97.97 (4.74) 31.27 (8.40) 0.10 (0.41)4 144.0 (11.5) -106.09 (5.52) 23.66 (8.25) 0.02 (0.40)

> 4 148.3 (12.3) -110.31 (5.53) 17.50 (6.83) -0.04 (0.41)

Experiment(a) -111.2 (5.1) n.a. n.a.(a) Clark et al. PRB 2004




Analysis of 17O NMR parameter distributionKernel Density Estimate Approach

3 4 5 6 717O CQ / MHz

0

0,2

0,4

0,6

0,8

1

17O

η

3 4 5 6 717O CQ / MHz

0

0,2

0,4

0,6

0,8

1

17O

η

Introduction of a correlated 3D NMR parameter distribution:

p (CQ , η, δiso) = G (CQ − CQ)× G (η − fη(CQ))× G (δiso − fδ(CQ))




Quantitative Analysis of 17O Experimental data

-120-80-400408017O δMAS / ppm

-60

-40

-20

0

20

40

17O

δIS

O /

ppm

DAS @ 9.4 T

Experiment


-120-80-400408017O δMAS / ppm

-60

-40

-20

0

20

40

17O

δIS

O /

ppm

DAS @ 9.4 T

Fit

Charpentier et al. JPC 2009

Experimental data can be well described in term of disorder only.




Interpretation of 17O Experimental data

17O NMR parameter distribution

Charpentier et al. JPC 2009 Clark et al. PRB 2004Mean Std. dev. Mean Std. dev.

Cq 5.07 MHz 0.453 MHz 5.08 MHz 0.372 MHzηq 0.157 0.095 0.150 0.0414δiso 36.5 ppm 7.55 ppm 36.7 ppm 4.30 ppm

Local geometry

JPC 2009 PRB 2004 Diffraction.Mean Std. dev. Mean Std. dev. Mean Std. dev.

Si-O-Si 147.1 11.17 146.6 3.78 148.3 7.5

Si-O 1.60 A 0.011 A 1.58 A 0.019 A 1.61 A 0.049 A




Bond Angle Distribution (BAD) T. Charpentier et al., J. Phys. Chem. C 2009

NMR / Structure relationships




Advanced NMR: Through Bond Correlation Spectroscopy29Si-17O J-HMQC experiments. GIPAW J Calc. coll. J. Yates Oxford

3456717O CQ / MHz

-140

-130

-120

-110

-100

-90

-80

-70

29Si

δis

o / pp

m

-40-200204017O δ / ppm

-130

-120

-110

-100

-9029

Si δ

/ pp

m

2D NMR enables the observation of spin pair 29Si-17O through thechemical bond (or through the space)⇒ Observation of Bond Angle θi − θi+1 correlation . . .




Topology of vitreous B2O3 G. Ferlat, T. Charpentier et al., PRL 2008




Topology of vitreous B2O3

0 10 20 30

q / A-1

0

0,5

1

1,5

2

S(q)

/ ar

b. u

nits

ExpMD

fring = 22%

0 10 20 30

q / A-1

0

0,5

1

1,5

2

S(q)

/ ar

b. u

nits

ExpMD

fring = 75%

S(q): poor sensitivity to Bond Angle ?




Topology of vitreous B2O3

-400-200020040017O chemical shift / ppm

ExpMD

fring = 22%

O(ring)

O(non-ring)

-400-200020040017O chemical shift / ppm

ExpMD

fring = 75%

O(ring)

O(non-ring)

NMR: high sensitivity to Bond Angle




aiNMR: PerspectivesA new powerfull tools to get more insight into NMR data



Ackwnowledgement

MD-GIPAW

L. Truflandier (LSDRM, Post-Doc)

Nuclear Waste Glasses

F. Angeli, P. Jollivet, S. Peuget, J.M. Delaye (CEA Valrho)

A. Quintas, D. Caurant, O. Majerus (ENS Chimie Paris)

MD simulations

S. Ispas (LCVN,Montpellier 2)

G. Ferlat (IMPMC, Paris 6)

P. Kroll (Arlington, Texas)

GIPAW

A. Seitsonen, F. Mauri (IMPMC, Paris 6)

J.Yates (Oxford)

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