Controlling and understanding local structure in supercooled liquidsfernique/geomateriaux2/... ·...
Transcript of Controlling and understanding local structure in supercooled liquidsfernique/geomateriaux2/... ·...
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December 2019
Controlling and understanding local structure in supercooled liquids
Susana Marín Aguilar
Rik Wensink
Frank Smallenburg
Giuseppe Foffi
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Overview1. Introduction
1.1 What is a glass?
1.2 How to model glasses/supercooled liquids?
2. How to control dynamics (or local structure)?
2.1 Interactions
2.2 Change on shape
2.3 Size distribution
3. Conclusions
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Temperature
Avoiding crystallization Glass
What is a glass?
Liquid
• No long range order
• Out of equilibrium• Arrested system
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Glass
When can we call it a glass?
Intermediate Scattering Function
Liquid Regime
Relaxation Time
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Glass
When can we call it a glass?
Intermediate Scattering Function
Relaxation Time
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Glass
When can we call it a glass?
Intermediate Scattering Function
Relaxation Time
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Glass
When can we call it a glass?
Intermediate Scattering Function
Relaxation Time
Cage Effect
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Glass
When can we call it a glass?
Intermediate Scattering Function
Relaxation Time
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Glass
When can we call it a glass?
Intermediate Scattering Function
Relaxation Time
Glass
Supercooledliquid
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Glass
When can we call it a glass?
Intermediate Scattering Function
Relaxation Time
Packing FractionR
ela
xati
on
Tim
e At least 4 orders of magnitude
Why?
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Local Structural Changes
Frank, P. ROY. SOC. A-MATH PHY, 215, 1120 (1952)
1952
Icosahedral Cluster
FCC HCP
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Local Structural Changes
Frank, P. ROY. SOC. A-MATH PHY, 215, 1120 (1952)
1952Icosahedral Cluster
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Local Structural Changes
Frank, P. ROY. SOC. A-MATH PHY, 215, 1120 (1952)
1952Icosahedral Cluster
Haller, et al. Nat. Commun., 9, 1,(2018)
Icosahedral Cluster
Defective Icosahedral
Cluster
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Local Structural Changes
Frank, P. ROY. SOC. A-MATH PHY, 215, 1120 (1952)
1952Icosahedral Cluster
Haller, et al. Nat. Commun., 9, 1,(2018)
Icosahedral Cluster
Defective Icosahedral
Cluster
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Local Structural Changes
Frank, P. ROY. SOC. A-MATH PHY, 215, 1120 (1952)
1952Icosahedral Cluster
Haller, et al. Nat. Commun., 9, 1,(2018)
Icosahedral Cluster
Defective Icosahedral
Cluster
9B
10B 12B
12D …
Other cluster with similar trends:
Malins, et al. JCP 139, 234506 (2013)
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How can we study glasses/supercooled liquids?
Simulations• Molecular
Dynamics
• Monte Carlo
Interaction PotentialHow the particles interact between each
other
Hung, et al. Soft Matter, 15, 6,(2019)
Atomistic modelsColloidal particles
• Lennard-Jones• Square-Well• Hard-spheres
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How can we study glasses/supercooled liquids?
Simulations• Molecular
Dynamics
• Monte Carlo
Interaction PotentialHow the particles interact between each
other
Colloidal particles
• Lennard-Jones• Square-Well• Hard-spheres
Event-Driven Molecular DynamicsEDMD
1. Initial configuration (positions and velocities)
2. Find the next time where two particles will collide
3. Solve collision4. Update velocities and
positions
STEPS:
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How can we study glasses/supercooled liquids?
Simulations• Molecular
Dynamics
• Monte Carlo
Interaction PotentialHow the particles interact between each
other
• Dynamical properties: diffusion coefficient, mean square displacement, relaxation times, ISF, ...
• Static properties: S(q), g(r), compresibility…
RESULTS:
Colloidal particles
• Lennard-Jones• Square-Well• Hard-spheres λ
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Short range potentials:
Repulsive glass:
Particles trapped by repulsionsfrom their neighbors.
Two glassy states
Tem
pe
ratu
re
Tem
pe
ratu
rePacking Fraction
F. Sciortino, Nat. Mater. (2002)
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Short range potentials: Two glassy states
Tem
pe
ratu
reIntermediate fluid:
Some particles tightly bound to neighbors, others more free to move.
F. Sciortino, Nat. Mater. (2002)
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Short range potentials:
Attractive glass:
Particles trapped by attractions to their neighbors.
Two glassy states
Tem
pe
ratu
re
F. Sciortino, Nat. Mater. (2002)
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Short range potentials: Two glassy states
Temperature
F. Sciortino, Nat. Mater. (2002)
Zaccarelli et al., PRE 66, 041402 (2002)
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Short range potentials: Two glassy states
Temperature
F. Sciortino, Nat. Mater. (2002)
Zaccarelli et al., PRE 66, 041402 (2002)
Attractive
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Short range potentials: Two glassy states
Temperature
F. Sciortino, Nat. Mater. (2002)
Zaccarelli et al., PRE 66, 041402 (2002)
Attractive Repulsive
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Colloids: ideal playground for studying glasses.
Size distributionShape
Rossi et al., Soft Matter 7, 4139 (2011)
Kuijk et al., J. Am. Chem. Soc. 133, 2346 (2011)
Talapin et al.,Nature 461, 964 (2009)
Chen et al., Nature 469, 381 (2011)
Y. Wang et al., Nature 491, 51 (2012)
Surface chemistry
How to control dynamics (or local structure)?
What about the glassy regime?
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Colloids: ideal playground for studying glasses.
Size distributionShape
Rossi et al., Soft Matter 7, 4139 (2011)
Kuijk et al., J. Am. Chem. Soc. 133, 2346 (2011)
Talapin et al.,Nature 461, 964 (2009)
Chen et al., Nature 469, 381 (2011)
Y. Wang et al., Nature 491, 51 (2012)
Surface chemistry
How to control dynamics (or local structure)?
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Colloids: ideal playground for studying glasses.
Chen et al., Nature 469, 381 (2011)
Y. Wang et al., Nature 491, 51 (2012)
Surface chemistry
How to control dynamics (or local structure)?
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Directional Interactions
How to modify the cage?
Kern-Frenkel Model Patchy Particles
Hard spheres decorated with attractive square-well patches on the surface.
Two particles bond when:⚫ The distance between them is less than the potential range.
⚫ The line connecting them goes through a patch on both surfaces.
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How to?
Increasing patch size (θ)
Hard sphere Square well
Event-Driven Molecular Dynamics
• Binary mixture• N= 700• λ=1.03σ• q=0.833 (size ratio) Change patch size
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How to?
Event-Driven Molecular Dynamics
• Binary mixture• N= 700• λ=1.03σ• q=0.833 (size ratio)
n = 3(Triangle)
n = 4(Tetrahedron)
n= 6(Octahedron)
n = 12(Icosahedron)
Increasing number of patches (n)
n = 8(Rotated
square prism)
Change patch geometry
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Reentrance in patchy particle systems
Reentrance remains intact for patchy interactions.
6 patches(Octahedron)
SW
η=0.58
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Reentrance in patchy particle systems
Reentrance remains intact for patchy interactions.
6 patches(Octahedron)
SW
η=0.58
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Reentrance in patchy particle systems
Reentrance remains intact for patchy interactions.
6 patches(Octahedron)
SW
η=0.58
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Reentrance in patchy particle systems
Reentrance remains intact for patchy interactions.
6 patches(Octahedron)
SW
η=0.58
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Reentrance in patchy particle systems
Reentrance remains intact for patchy interactions.
6 patches(Octahedron)
SW
η=0.58
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Reentrance in patchy particle systems
Reentrance remains intact for patchy interactions.
6 patches(Octahedron)
SW
η=0.58
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Reentrance in patchy particle systems
Reentrance remains intact for patchy interactions.
6 patches(Octahedron)
SW
η=0.58
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What is the behavior with different geometries?
Fixed surface coverage of 40%
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What is the behavior with different geometries?
Fixed surface coverage of 40%
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What is the behavior with different geometries?
Fixed surface coverage of 40%
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What is the behavior with different geometries?
Fixed surface coverage of 40%
Drastic slowdown for10, 11, and 12 patches.
What about the local structure?
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Topological Cluster Classification
Malins, A., et al. J. Chem Phys, 139, 23 (2013)
Modified Voronoi construction that:
• Prevents counting the particles in the second shell.
• Allows distorted 4 ring members.
“Direct neighbours “
…
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Fraction of particles involved in an icosahedral cage.
Why 10, 11 and 12 patches are so special ?
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Fraction of particles involved in an icosahedral cage.
Why 10, 11 and 12 patches are so special ?
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Fraction of particles involved in an icosahedral cage.
Why 10, 11 and 12 patches are so special ?
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Fraction of particles involved in an icosahedral cage.
Why 10, 11 and 12 patches are so special ?
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Why 10, 11 and 12 patches are so special ?
Fraction of particles involved in an icosahedral cage.
10, 11 and 12 patch case reinforce
icosahedral order at low temperature
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Why 10, 11 and 12 patches are so special ?
Fraction of particles involved in an icosahedral cage.10, 11 and 12
patch case reinforce
icosahedral order at low temperature
By adding directionality tointeractions, there is a wayof changing the structureof the cages by reinforcingthe geometries that matchwith long-lived structures.
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Why 10, 11 and 12 patches are so special ?
Fraction of particles involved in an icosahedral cage.
Patchy interactions play a major role
What can wedo here?
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Colloidal glasses and how to model them?
Shape
Rossi et al., Soft Matter 7, 4139 (2011)
Kuijk et al., J. Am. Chem. Soc. 133, 2346 (2011) Patchy interactions play a major role
What can wedo here?
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Shape
Rossi et al., Soft Matter 7, 4139 (2011)
Kuijk et al., J. Am. Chem. Soc. 133, 2346 (2011)
Colloidal glasses and how to model them?
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Shape
Surface chemistry
• Directional interactions can induce changes inthe local structure.
• The enhancement of icosahedral clusterspromotes a slowing down on dynamics in patchyparticles and polyhedral repulsive particles.
• The reentrance is conserved in systems ofpatchy particles.
• Systems with same coverage behave the sameexcepting for the ones that enhance specific localstructures.
Slowing down supercooled liquids by manipulating their local structures
arXiv:1812.00764
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Colloids: ideal playground for studying glasses.
Size distributionShape
Rossi et al., Soft Matter 7, 4139 (2011)
Kuijk et al., J. Am. Chem. Soc. 133, 2346 (2011)
Talapin et al.,Nature 461, 964 (2009)
Chen et al., Nature 469, 381 (2011)
Y. Wang et al., Nature 491, 51 (2012)
Surface chemistry
Colloidal glasses and how to model them?
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Hard Sphere Systems
Palangetic et al., Faraday discussions, 191, 325 (2016)
• Purely repulsive interactions• Capture changes on dynamics towards
the glass regime
How to avoid?
Using mixtures of different size ratios
Theory
Experiments
Simulations
Packing Fraction
Supercooled liquid regime
Parisi et al., JSTAT, 2009, 03 (2009)
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Hard Sphere Systems
Palangetic et al., Faraday discussions, 191, 325 (2016)
Packing FractionParisi et al., JSTAT, 2009, 03 (2009)
Supercooled liquid regime
Binary Mixtures
Polydisperse Systems
Change size ratio q (from 0.6 to 0.8)Change in composition xL (from 0.2 to 0.65)
Change polydispersity from 2% - 8%
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Dynamics (Binary Mixtures)Diffu
sion
tim
e
η=0.575
Composition (Large Particles)
Size ratioσB/σA
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Dynamics (Binary Mixtures)Diffu
sion
tim
e • Non monotonous behaviouron dynamics by changing sizeratio and composition.
η=0.575
Composition (Large Particles)
Size ratioσB/σA
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Dynamics and Structure
η=0.575 Number of particles in Icosahedral Clusters
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Tetrahedrality
Tetrahedron: smallest
cluster in 3 dimensions.
Tetrahedral cluster: 4 neighbour particles linked all together by distance.
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Tetrahedrality
Tetrahedron: smallest
cluster in 3 dimensions.
Tetrahedral cluster: 4 neighbour particles linked all together by distance.
Quantify the tetrahedrality of the local structure:
Counting the number of tetrahedron that one particle is involved in.
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Tetrahedrality
Tetrahedron: smallest
cluster in 3 dimensions.
Tetrahedral cluster: 4 neighbour particles linked all together by distance.
Quantify the tetrahedrality of the local structure:
Counting the number of tetrahedron that one particle is involved in.
Icosahedral Cluster
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Tetrahedrality
Tetrahedron: smallest
cluster in 3 dimensions.
Tetrahedral cluster: 4 neighbour particles linked all together by distance.
Quantify the tetrahedrality of the local structure:
Counting the number of tetrahedron that one particle is involved in.
Icosahedral Cluster
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Tetrahedrality
Tetrahedron: smallest
cluster in 3 dimensions.
Tetrahedral cluster: 4 neighbour particles linked all together by distance.
Quantify the tetrahedrality of the local structure:
Counting the number of tetrahedron that one particle is involved in.
Icosahedral Cluster
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Tetrahedrality
Tetrahedron: smallest
cluster in 3 dimensions.
Tetrahedral cluster: 4 neighbour particles linked all together by distance.
Quantify the tetrahedrality of the local structure:
Counting the number of tetrahedron that one particle is involved in.
Icosahedral Cluster
![Page 65: Controlling and understanding local structure in supercooled liquidsfernique/geomateriaux2/... · 2019-12-18 · How can we study glasses/supercooled liquids? Simulations •Molecular](https://reader033.fdocuments.us/reader033/viewer/2022050402/5f806701c23bb052212ca73a/html5/thumbnails/65.jpg)
Tetrahedrality
Tetrahedron: smallest
cluster in 3 dimensions.
Tetrahedral cluster: 4 neighbour particles linked all together by distance.
Quantify the tetrahedrality of the local structure:
Counting the number of tetrahedron that one particle is involved in.
Icosahedral Cluster
![Page 66: Controlling and understanding local structure in supercooled liquidsfernique/geomateriaux2/... · 2019-12-18 · How can we study glasses/supercooled liquids? Simulations •Molecular](https://reader033.fdocuments.us/reader033/viewer/2022050402/5f806701c23bb052212ca73a/html5/thumbnails/66.jpg)
Tetrahedrality
Tetrahedron: smallest
cluster in 3 dimensions.
Tetrahedral cluster: 4 neighbour particles linked all together by distance.
Quantify the tetrahedrality of the local structure:
Counting the number of tetrahedron that one particle is involved in.
Icosahedral Cluster
![Page 67: Controlling and understanding local structure in supercooled liquidsfernique/geomateriaux2/... · 2019-12-18 · How can we study glasses/supercooled liquids? Simulations •Molecular](https://reader033.fdocuments.us/reader033/viewer/2022050402/5f806701c23bb052212ca73a/html5/thumbnails/67.jpg)
Tetrahedrality
Tetrahedron: smallest
cluster in 3 dimensions.
Tetrahedral cluster: 4 neighbour particles linked all together by distance.
Quantify the tetrahedrality of the local structure:
Counting the number of tetrahedron that one particle is involved in.
Icosahedral Cluster
![Page 68: Controlling and understanding local structure in supercooled liquidsfernique/geomateriaux2/... · 2019-12-18 · How can we study glasses/supercooled liquids? Simulations •Molecular](https://reader033.fdocuments.us/reader033/viewer/2022050402/5f806701c23bb052212ca73a/html5/thumbnails/68.jpg)
Tetrahedrality
Tetrahedron: smallest
cluster in 3 dimensions.
The central particle will be involved in 20 tetrahedrons
Tetrahedral cluster: 4 neighbour particles linked all together by distance.
Quantify the tetrahedrality of the local structure:
Counting the number of tetrahedron that one particle is involved in.
Icosahedral Cluster
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η=0.575 Number of tetrahedron per particle
Dynamics and Structure
• Non monotonous behaviouron average number oftetrahedron per particle.
• Sensitive parameter to thechanges of q and XL
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η=0.575 Number of tetrahedron per particle
Dynamics and Structure
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Hard Sphere Systems
Number of tetrahedron per particle
Diffu
sion
tim
e
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Hard Sphere Systems
Different packing fractions follow the
same relation between the number of
tetrahedra and the diffusion time.
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Hard Sphere Systems
Different packing fractions follow the
same relation between the number of
tetrahedra and the diffusion time.
The polydisperse systems follow the
same trend.
General Behavior
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Heterogeinity
Local Behavior
Regions of high mobility
Regions of low mobility
Tanaka, et al. Nat. mater, 9, 4, (2010)
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Heterogeinity
Local Behavior
How the tetrahedrality of the system affects local mobility?
Characterize:• Local mobility (Propensity)
• Local tetrahedrality
Correlation
Tanaka, et al. Nat. mater, 9, 4, (2010)
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Hard Sphere Systems
How well correlated are those two quantities in time?
Number of tetrahedra
TETRAHEDRALITY
MOBILITY
Anticorrelation
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Hard Sphere Systems
How well correlated are those two quantities in time?
Number of tetrahedra
TETRAHEDRALITY
MOBILITY
Propensity
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Hard Sphere Systems
How well correlated are those two quantities in time?
Number of tetrahedra
TETRAHEDRALITY
MOBILITY
Propensity
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Hard Sphere Systems
How well correlated are those two quantities in time?
Propensity Number of tetrahedra
TETRAHEDRALITY
MOBILITY
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Hard Sphere Systems
How well correlated are those two quantities in time?
Number of tetrahedra
TETRAHEDRALITY
MOBILITY
Propensity
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Hard Sphere SystemsTETRAHEDRALITY
MOBILITY
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Summary (second part)
• Changing the size ratio and the composition induces changes in thelocal structure and the dynamics.
• Tetrahedrality is a good parameter that can be used to predict globaldynamical properties.
• At a local level, regions with high tetrahedrality are less mobile.
Tetrahedrality dictates dynamics in hard spheresarXiv:1908.00425
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Thank you!
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Different Patch Geometries
The number of bonds obeys a master curve, when the temperature is normalized.
Number of bonds per particle
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Different Patch Geometries
Number of bonds per particle
Then… what about the local structure?